Three-dimensional printing

ABSTRACT

An example of a three-dimensional (3D) printing kit includes a build material composition and a fusing agent to be applied to at least a portion of the build material composition during 3D printing. The build material composition includes a thermoplastic elastomer having: an avalanche angle ranging from about 49 degrees to about 59 degrees; a break energy ranging from about 55 kJ/kg to about 78 kJ/kg; and an avalanche energy ranging from about 10 kJ/kg to about 27 kJ/kg. The fusing agent includes an energy absorber to absorb electromagnetic radiation to coalesce the thermoplastic elastomer in the at least the portion.

BACKGROUND

Three-dimensional (3D) printing may be an additive printing process usedto make three-dimensional solid parts from a digital model. 3D printingis often used in rapid product prototyping, mold generation, mold mastergeneration, and short run manufacturing. Some 3D printing techniques areconsidered additive processes because they involve the application ofsuccessive layers of material (which, in some examples, may includebuild material, binder and/or other printing liquid(s), or combinationsthereof). This is unlike traditional machining processes, which oftenrely upon the removal of material to create the final part. Some 3Dprinting methods use chemical binders or adhesives to bind buildmaterials together. Other 3D printing methods involve at least partialcuring, thermal merging/fusing, melting, sintering, etc. of the buildmaterial, and the mechanism for material coalescence may depend upon thetype of build material used. For some materials, at least partialmelting may be accomplished using heat-assisted extrusion, and for someother materials (e.g., polymerizable materials), curing or fusing may beaccomplished using, for example, ultra-violet light or infrared light.

BRIEF DESCRIPTION OF THE DRAWINGS

Features of examples of the present disclosure will become apparent byreference to the following detailed description and drawings, in whichlike reference numerals correspond to similar, though perhaps notidentical, components. For the sake of brevity, reference numerals orfeatures having a previously described function may or may not bedescribed in connection with other drawings in which they appear.

FIG. 1 is a flow diagram illustrating an example of a method for 3Dprinting;

FIG. 2 is a flow diagram illustrating another example of a method for 3Dprinting;

FIG. 3 is a cross-sectional view of an example of a part formed using anexample of the 3D printing methods disclosed herein;

FIGS. 4A through 4H are schematic views depicting the formation of apart using an example of the 3D printing methods disclosed herein;

FIGS. 5A through 5C are schematic views depicting the formation of apart using another example of the 3D printing methods disclosed herein;

FIGS. 6A and 6B are schematic views depicting the formation of a partusing still another example of the 3D printing methods disclosed herein;and

FIG. 7 is a simplified isometric and schematic view of an example of a3D printing system disclosed herein.

DETAILED DESCRIPTION

Some examples of three-dimensional (3D) printing may utilize a fusingagent (including an energy absorber) to pattern polymeric buildmaterial. In these examples, an entire layer of the polymeric buildmaterial is exposed to radiation, but the patterned region (which, insome instances, is less than the entire layer) of the polymeric buildmaterial is coalesced/fused and hardened to become a layer of a 3Dobject. In the patterned region, the fusing agent is capable of at leastpartially penetrating into voids between the polymeric build materialparticles, and is also capable of spreading onto the exterior surface ofthe polymeric build material particles. This fusing agent is capable ofabsorbing radiation and converting the absorbed radiation to thermalenergy, which in turn coalesces/fuses the polymeric build material thatis in contact with the fusing agent. Coalescing/fusing causes thepolymeric build material to join or blend to form a single entity (i.e.,the layer of the 3D object). Coalescing/fusing may involve at leastpartial thermal merging, melting, binding, and/or some other mechanismthat coalesces the polymeric build material to form the layer of the 3Dobject.

In these examples of 3D printing, the polymeric build material, thefusing agent, the radiation exposure process, etc., may be selected sothat the patterned build material is able to coalesce/fuse to form amechanically strong 3D object, while the non-patterned build materialremains non-coalesced/non-fused when exposed to the radiation. Somepolymeric build materials, which may be used in other fabricationmethods (e.g., injection molding, selective laser sintering (SLS),selective laser melting (SLM), etc.), may be incompatible with thefusing agent and/or the radiation exposure process. For example, somepolymeric build materials may be unable to sufficiently coalesce/fuse toform a mechanically strong 3D object when patterned with the fusingagent and exposed to the radiation. For another example, some polymericbuild materials may over coalesce/fuse when patterned with the fusingagent and exposed to the radiation, which can form a brittle 3D object.

Further, some polymeric build materials, which may be used in otherfabrication methods, may have insufficient flowability and may be unableto be spread into substantially uniform build material layers. Buildmaterial layers that are not substantially uniform may cause theformation of voids within the 3D object, which may deleteriously affectthe mechanical strength of the 3D object. Further, insufficientspreading of the build material may cause over coalescing/fusing, whichmay form a brittle 3D object. Build material layers that are notsubstantially uniform may also deleteriously affect the surface finishquality and/or accuracy of the 3D object. For example, the surface maybe undesirably rough and/or may have an undesirable appearance. Asanother example, the 3D object or regions thereof may be larger orsmaller than intended.

Build Material Compositions

Disclosed herein is a build material composition that includes athermoplastic elastomer having: an avalanche angle ranging from about 49degrees to about 59 degrees; a break energy ranging from about 55 kJ/kgto about 78 kJ/kg; and an avalanche energy ranging from about 10 kJ/kgto about 27 kJ/kg.

As used herein, the “avalanche angle” refers to the angle of thethermoplastic elastomer powder sample at the maximum power prior to thestart of an avalanche occurrence. Also as used herein, the “breakenergy” is the amount of energy a thermoplastic elastomer powder samplein a rotating drum can accumulate before a powder avalanche occurs.Still further, as used herein, the “avalanche energy” is the energy thatis lost as a result of an avalanche occurrence. In other words, theavalanche energy may be the difference between the break energy and theenergy after the avalanche occurrence is over and the thermoplasticelastomer powder sample is at rest. The avalanche energy may be referredto as the energy between thermoplastic elastomer stick and slip eventsduring avalanching.

It has been found that thermoplastic elastomers with thesecharacteristics are compatible with the fusing agent and/or theradiation exposure process disclosed herein. These thermoplasticelastomers are able to sufficiently fuse/coalesce to form a mechanicallystrong 3D object when patterned with the fusing agent and exposed to theradiation. Further, these thermoplastic elastomers have sufficientflowability and are able to be spread into substantially uniform buildmaterial layers. As such, the thermoplastic elastomers disclosed hereintend to not over-fuse/coalesce or under-fuse/coalesce. Therefore, thesethermoplastic elastomer build materials may be successfully used incommercially available 3D printers (i.e., those that utilize fusingagent(s) and radiation exposure) to generate mechanically strong 3Dobjects, without having to make adjustments to the mechanical parts ofthe printer (e.g., to achieve spreading) and/or the printing agents ofthe printer. The energy exposure settings of the printer may or may notbe adjusted, depending, in part on the type of build material that hadpreviously been used in the printer.

In some examples, the build material composition consists of thethermoplastic elastomer. In other examples, the build materialcomposition may include additional components, such as an antioxidant, awhitener, an antistatic agent, a flow aid, or a combination thereof.

The thermoplastic elastomer may be any thermoplastic elastomer that hasan avalanche angle ranging from about 49 degrees to about 59 degrees; abreak energy ranging from about 55 kJ/kg to about 78 kJ/kg; and anavalanche energy ranging from about 10 kJ/kg to about 27 kJ/kg. In someexamples, the thermoplastic elastomer is selected from the groupconsisting of a thermoplastic polyamide (TPA), a thermoplasticpolyurethane (TPU), a styrenic block copolymer (TPS), a thermoplasticpolyolefin elastomer (TPO), a thermoplastic vulcanizate (TPV),thermoplastic copolyester (TPC), and a combination thereof. In otherexamples, the thermoplastic elastomer is selected from the groupconsisting of a thermoplastic polyamide, a thermoplastic polyurethane,and a combination thereof. In still other examples, the thermoplasticelastomer is a polyether block amide (PEBA). In yet other examples, thethermoplastic elastomer is a thermoplastic polyurethane.

Polyether block amide elastomers may be obtained by the polycondensationof a carboxylic acid terminated polyamide (PA 6, PA 11, PA 12) with analcohol terminated polyether (e.g., polytetramethylene glycol (PTMG),polyethylene glycol (PEG), etc.). Two examples of commercially availablePEBA elastomers include those known under the tradename of PEBAX®(Arkema) and VESTAMID® E (Evonik Industries).

Thermoplastic polyurethane elastomers may be obtained by reaction of:(i) diisocyanates with short-chain diols (so-called chain extenders)and/or (ii) diisocyanates with long-chain diols. Two examples ofcommercially available TPU elastomers include those known under thetradename of DESMOPAN® (Covestro) and ELASTOLLAN® (BASF Corp.).

As mentioned above, the thermoplastic elastomer has an avalanche angleranging from about 49 degrees to about 59 degrees. In an example, thethermoplastic elastomer is a polyether block amide and the avalancheangle ranges from about 55 degrees to about 59 degrees. In anotherexample, the thermoplastic elastomer is a polyether block amide and theavalanche angle is about 57 degrees. In still another example, thethermoplastic elastomer is a thermoplastic polyurethane and theavalanche angle ranges from about 49 degrees to about 53 degrees. In yetanother example, the thermoplastic elastomer is a thermoplasticpolyurethane and the avalanche angle is about 51 degrees.

Also as mentioned above, the thermoplastic elastomer has a break energyranging from about 55 kJ/kg to about 78 kJ/kg. In an example, thethermoplastic elastomer is a polyether block amide and the break energyranges from about 68 kJ/kg to about 78 kJ/kg. In another example, thethermoplastic elastomer is a polyether block amide and the break energyis about 73 kJ/kg. In still another example, the thermoplastic elastomeris a thermoplastic polyurethane and the break energy ranges from about55 kJ/kg to about 65 kJ/kg. In yet another example, the thermoplasticelastomer is a thermoplastic polyurethane and the break energy is about60 kJ/kg.

Still further, as mentioned above, the thermoplastic elastomer has anavalanche energy ranging from about 10 kJ/kg to about 27 kJ/kg. In anexample, the thermoplastic elastomer is a polyether block amide and theavalanche energy ranges from about 17 kJ/kg to about 27 kJ/kg. Inanother example, the thermoplastic elastomer is a polyether block amideand the avalanche energy is about 22 kJ/kg. In still another example,the thermoplastic elastomer is a thermoplastic polyurethane and theavalanche energy ranges from about 10 kJ/kg to about 20 kJ/kg. In yetanother example, the thermoplastic elastomer is a thermoplasticpolyurethane and the avalanche energy is about 15 kJ/kg.

In some examples, the thermoplastic elastomer further has a dynamicdensity within about 15% of a bulk density of the thermoplasticelastomer. In other words, the thermoplastic elastomer may have adynamic density that is ±(plus or minus) about 15% of the bulk densityof the thermoplastic elastomer. The dynamic density is the density ofthe thermoplastic elastomer while the thermoplastic elastomer isrotating in a drum or cylinder.

In some examples, the dynamic density of the thermoplastic elastomer mayrange from about 0.3 g/cc to about 0.5 g/cc. In an example, thethermoplastic elastomer is a polyether block amide having a dynamicdensity of about 0.36 g/cc. In another example, the thermoplasticelastomer is a thermoplastic polyurethane having a dynamic density ofabout 0.34 g/cc.

Each of these properties (i.e., the avalanche angle, the break energy,the avalanche energy, and the dynamic density) may be measured in aninstrument, such as the REVOLUTION™ Powder Analyzer from MercuryScientific Inc. This type of instrument includes a drum that rotates thepowder (at a user selected revolution rate and for a user selectedtime), and collects digital images of the powder during the rotationprocess. This instrument measures the behavior of the powder from thedigital images. Instruments that are capable of measuring theseproperties may analyze samples ranging from 10 cubic centimeters (cc orcm³) to 500 cc at a rotation (or revolution) rate ranging from 0.1rotations per minute (RPM) to 200 RPM, an imaging rate of up 30 framesper second (FPS), and a prep time ranging from 0 seconds to 999 seconds.These instruments may also be capable of measuring the properties ofpowders at room temperature (e.g., a temperature ranging from about 18°C. to about 25° C.) or at temperatures above 25° C. and up to 200° C. Inan example, the avalanche angle, the break energy, the avalanche energy,and/or the dynamic density of the thermoplastic elastomer may bemeasured over 100 avalanches at room temperature (e.g., a temperatureranging from about 18° C. to about 25° C.) using a 100 cc sample of thethermoplastic elastomer, a rotation (or revolution) rate of 0.3 RPM, animaging rate of 10 FPS, a prep time of 60 seconds, and an avalanchethreshold of 0.65%. While the properties of the thermoplastic elastomermay be analyzed using other parameters, it is to be understood that, asused herein, any avalanche angle, any break energy, any avalancheenergy, and any dynamic density is in relation to 100 avalanches at roomtemperature using a 100 cc sample of the thermoplastic elastomer, arotation (or revolution) rate of 0.3 RPM, an imaging rate of 10 FPS, aprep time of 60 seconds, and an avalanche threshold of 0.65%.

In some examples, the thermoplastic elastomer may be in the form of apowder. In other examples, the thermoplastic elastomer may be in theform of a powder-like material, which includes, for example, shortfibers having a length that is greater than its width. In some examples,the powder or powder-like material may be formed from, or may include,short fibers that may, for example, have been cut into short lengthsfrom long strands or threads of material.

The thermoplastic elastomer may be made up of similarly sized particlesand/or differently sized particles. In an example, the average particlesize of the thermoplastic elastomer ranges from about 2 μm to about 225μm. In another example, the average particle size of the thermoplasticelastomer ranges from about 10 μm to about 130 μm. The term “averageparticle size”, as used herein, may refer to a number-weighted meandiameter or a volume-weighted mean diameter of a particle distribution.

In some other examples, the thermoplastic elastomer may have a meltingrange within the range of from about 130° C. to about 250° C. In someexamples (e.g., when the thermoplastic elastomer is a polyether blockamide), the thermoplastic elastomer may have a melting range of fromabout 130° C. to about 175° C. In some other examples (e.g., when thethermoplastic elastomer is a thermoplastic polyurethane), thethermoplastic elastomer may have a melting range of from about 130° C.to about 180° C. or a melting range of from about 175° C. to about 210°C.

In some examples, the thermoplastic elastomer does not substantiallyabsorb radiation having a wavelength within the range of 400 nm to 1400nm. In other examples, the thermoplastic elastomer does notsubstantially absorb radiation having a wavelength within the range of800 nm to 1400 nm. In still other examples, the thermoplastic elastomerdoes not substantially absorb radiation having a wavelength within therange of 400 nm to 1200 nm. In these examples, the thermoplasticelastomer may be considered to reflect the wavelengths at which thethermoplastic elastomer does not substantially absorb radiation. Thephrase “does not substantially absorb” means that the absorptivity ofthe thermoplastic elastomer at a particular wavelength is 25% or less(e.g., 20%, 10%, 5%, etc.).

In some examples, the build material composition, in addition to thethermoplastic elastomer, may include an antioxidant, a whitener, anantistatic agent, a flow aid, or a combination thereof. While severalexamples of these additives are provided, it is to be understood thatthese additives are selected to be thermally stable (i.e., will notdecompose) at the 3D printing temperatures.

Antioxidant(s) may be added to the build material composition to preventor slow molecular weight decreases of the thermoplastic elastomer and/ormay prevent or slow discoloration (e.g., yellowing) of the thermoplasticelastomer by preventing or slowing oxidation of the thermoplasticelastomer. In some examples, the antioxidant may discolor upon reactingwith oxygen, and this discoloration may contribute to the discolorationof the build material composition. The antioxidant may be selected tominimize discoloration. In some examples, the antioxidant may be aradical scavenger. In these examples, the antioxidant may includeIRGANOX® 1098 (benzenepropanamide,N,N-1,6-hexanediylbis(3,5-bis(1,1-dimethylethyl)-4-hydroxy)), IRGANOX®254 (a mixture of 40% triethylene glycolbis(3-tert-butyl-4-hydroxy-5-methylphenyl), polyvinyl alcohol anddeionized water), and/or other sterically hindered phenols. In otherexamples, the antioxidant may include a phosphite and/or an organicsulfide (e.g., a thioester). The antioxidant may be in the form of fineparticles (e.g., having an average particle size of 5 μm or less) thatare dry blended with the thermoplastic elastomer. In an example, theantioxidant may be included in the build material composition in anamount ranging from about 0.01 wt % to about 5 wt %, based on the totalweight of the build material composition. In other examples, theantioxidant may be included in the build material composition in anamount ranging from about 0.01 wt % to about 2 wt % or from about 0.2 wt% to about 1 wt %, based on the total weight of the build materialcomposition.

Whitener(s) may be added to the build material composition to improvevisibility. Examples of suitable whiteners include titanium dioxide(TiO₂), zinc oxide (ZnO), calcium carbonate (CaCO₃), zirconium dioxide(ZrO₂), aluminum oxide (Al₂O₃), silicon dioxide (SiO₂), boron nitride(BN), and combinations thereof. In some examples, a stilbene derivativemay be used as the whitener and a brightener. In these examples, thetemperature(s) of the 3D printing process may be selected so that thestilbene derivative remains stable (i.e., the 3D printing temperaturedoes not thermally decompose the stilbene derivative). In an example,any example of the whitener may be included in the build materialcomposition in an amount ranging from greater than 0 wt % to about 10 wt%, based on the total weight of the build material composition.

Antistatic agent(s) may be added to the build material composition tosuppress tribo-charging. Examples of suitable antistatic agents includealiphatic amines (which may be ethoxylated), aliphatic amides,quaternary ammonium salts (e.g., behentrimonium chloride orcocamidopropyl betaine), esters of phosphoric acid, polyethyleneglycolesters, or polyols. Some suitable commercially availableantistatic agents include HOSTASTAT® FA 38 (natural based ethoxylatedalkylamine), HOSTASTAT® FE2 (fatty acid ester), and HOSTASTAT® HS 1(alkane sulfonate), each of which is available from Clariant Int. Ltd.).In an example, the antistatic agent is added in an amount ranging fromgreater than 0 wt % to less than 5 wt %, based upon the total weight ofthe build material composition.

Flow aid(s) may be added to improve the coating flowability of the buildmaterial composition. Flow aids may be particularly beneficial when thebuild material composition has an average particle size less than 25 μm.The flow aid improves the flowability of the build material compositionby reducing the friction, the lateral drag, and the tribocharge buildup(by increasing the particle conductivity). Examples of suitable flowaids include aluminum oxide (Al₂O₃), tricalcium phosphate (E341),powdered cellulose (E460(ii)), magnesium stearate (E470b), sodiumbicarbonate (E500), sodium ferrocyanide (E535), potassium ferrocyanide(E536), calcium ferrocyanide (E538), bone phosphate (E542), sodiumsilicate (E550), silicon dioxide (E551), calcium silicate (E552),magnesium trisilicate (E553a), talcum powder (E553b), sodiumaluminosilicate (E554), potassium aluminum silicate (E555), calciumaluminosilicate (E556), bentonite (E558), aluminum silicate (E559),stearic acid (E570), and polydimethylsiloxane (E900). In an example, theflow aid is added in an amount ranging from greater than 0 wt % to lessthan 5 wt %, based upon the total weight of the build materialcomposition.

In some examples, the build material composition disclosed herein may bereused/recycled. After a print cycle, some of the build materialcomposition disclosed herein remains non-coalesced/non-fused, and can bereclaimed and used again. This reclaimed build material is referred toas the recycled build material composition. The recycled build materialcomposition may be exposed to 2, 4, 6, 8, 10, or more build cycles(i.e., heating to a temperature ranging from about 50° C. to about 160°C. and then cooling), and reclaimed after each cycle. Between cycles,the recycled build material composition may be mixed with at least somefresh or virgin (i.e., not previously used in a 3D printing process)build material composition. In some examples, the weight ratio of therecycled build material composition to the fresh build materialcomposition may be 90:10, 80:20, 70:30, 60:40, 50:50, or 40:60. Theweight ratio of the recycled build material composition to the freshbuild material composition may depend, in part, on the stability of thebuild material composition, the discoloration of the recycled buildmaterial composition (as compared to the build material composition),the desired aesthetics for the 3D object being formed, the thermaldecomposition of the recycled build material composition (as compared tothe build material composition), and/or the desired mechanicalproperties of the 3D object being formed.

3D Printing Kits and Compositions

The build material composition described herein may be part of a 3Dprinting kit and/or a 3D printing composition.

In an example, the three-dimensional (3D) printing kit, comprises: abuild material composition including a thermoplastic elastomer having:an avalanche angle ranging from about 49 degrees to about 59 degrees; abreak energy ranging from about 55 kJ/kg to about 78 kJ/kg; and anavalanche energy ranging from about 10 kJ/kg to about 27 kJ/kg; and afusing agent to be applied to at least a portion of the build materialcomposition during 3D printing, the fusing agent including an energyabsorber to absorb electromagnetic radiation to coalesce thethermoplastic elastomer in the at least the portion.

In some examples, the 3D printing kit consists of the build materialcomposition and the fusing agent with no other components. In otherexamples, the kit includes additional components, such as another fusingagent, a coloring agent, a detailing agent, or a combination thereof.The components of the kit may be maintained separately until usedtogether in examples of the 3D printing method disclosed herein.

Any example of the build material composition may be used in theexamples of the 3D printing kit. As mentioned above, the build materialcomposition includes at least the thermoplastic elastomer, and mayadditionally include the antioxidant, the whitener, the antistaticagent, the flow aid, or combinations thereof.

In an example of the 3D printing kit, the thermoplastic elastomer has adynamic density within about 15% of a bulk density of the thermoplasticelastomer.

In another example of the 3D printing kit, one of: (i) the thermoplasticelastomer is a polyether block amide, the avalanche angle ranges fromabout 55 degrees to about 59 degrees, the break energy ranges from about68 kJ/kg to about 78 kJ/kg, and the avalanche energy ranges from about17 kJ/kg to about 27 kJ/kg; or (ii) the thermoplastic elastomer is athermoplastic polyurethane, the avalanche angle ranges from about 49degrees to about 53 degrees, the break energy ranges from about 55 kJ/kgto about 65 kJ/kg, and the avalanche energy ranges from about 10 kJ/kgto about 20 kJ/kg.

In still another example, the thermoplastic elastomer is a polyetherblock amide having a dynamic density of about 0.36 g/cc.

The fusing agent in the printing kit includes at least the energyabsorber. In some examples, the fusing agent is a core fusing agent andthe energy absorber has absorption at least at wavelengths ranging from400 nm to 780 nm. The core fusing agent may also have absorption atwavelengths ranging from 800 nm to 4000 nm. In some of these examples,the 3D printing kit further includes a primer fusing agent including aplasmonic resonance absorber having absorption at wavelengths rangingfrom 800 nm to 4000 nm and having transparency at wavelengths rangingfrom 400 nm to 780 nm. In other examples, the fusing agent is a primerfusing agent and the energy absorber is a plasmonic resonance absorberhaving absorption at wavelengths ranging from 800 nm to 4000 nm andhaving transparency at wavelengths ranging from 400 nm to 780 nm.Example compositions of the fusing agent (e.g., example compositions ofthe core fusing and example compositions of the primer fusing agent) aredescribed below.

In some examples, the 3D printing kit further comprises a coloring agentselected from the group consisting of a black agent, a cyan agent, amagenta agent, and a yellow agent. In some of these examples, the 3Dprinting kit may include multiple coloring agents. For example, the 3Dprinting kit may include a coloring agent for each desired color (e.g.,black, cyan, magenta, yellow, etc.). Any of the example compositions ofthe coloring agent described below may be used in the examples of the 3Dprinting kit.

In some examples, the 3D printing kit further comprises a detailingagent including a surfactant, a co-solvent, and water. Any of theexample compositions of the detailing agent described below may be usedin the examples of the 3D printing kit.

In another example, the three-dimensional (3D) printing compositioncomprises: a build material including a thermoplastic elastomer having:an avalanche angle ranging from about 49 degrees to about 59 degrees; abreak energy ranging from about 55 kJ/kg to about 78 kJ/kg; and anavalanche energy ranging from about 10 kJ/kg to about 27 kJ/kg; and afusing agent to be applied to at least a portion of the build materialduring 3D printing, the fusing agent including an energy absorber havingabsorption at least at some wavelengths ranging from 400 nm to 4000 nmto absorb electromagnetic radiation to coalesce the thermoplasticelastomer in the at least the portion. In an example of the 3D printingcomposition, the thermoplastic elastomer has a dynamic density withinabout 15% of a bulk density of the thermoplastic elastomer.

As used herein, “material set” or “kit” may, in some instances, besynonymous with “composition.” Further, “material set” and “kit” areunderstood to be compositions comprising one or more components wherethe different components in the compositions are each contained in oneor more containers, separately or in any combination, prior to andduring printing but these components can be combined together duringprinting. The containers can be any type of a vessel, box, or receptaclemade of any material.

Fusing Agents

In the examples of the 3D printing kit, the 3D printing methods, and the3D printing system disclosed herein, a fusing agent may be used.

Some examples of the fusing agent have substantial absorption (e.g.,80%) at least in the visible region (400 nm-780 nm). These examples ofthe fusing agent are referred to as the core fusing agent, or, in someinstances, the black fusing agent. As described herein, the energyabsorber in the core fusing agent may also absorb energy in the infraredregion (e.g., 800 nm to 4000 nm). This absorption generates heatsuitable for coalescing/fusing during 3D printing, which leads to 3Dobjects (or 3D objects regions) having mechanical integrity andrelatively uniform mechanical properties (e.g., strength, elongation atbreak, etc.). This absorption, however, also results in stronglycolored, e.g., black, 3D objects (or 3D objects regions). In theseexamples of the fusing agent, the energy absorber may be referred to asthe active material.

Other examples of the fusing agent include a plasmonic resonanceabsorber having absorption at wavelengths ranging from 800 nm to 4000 nmand having transparency at wavelengths ranging from 400 nm to 780 nm.These examples of the fusing agent are referred to as the primer fusingagent, or, in some instances, the low tint fusing agent. This absorptionand transparency allows the primer fusing agent to absorb enoughradiation to coalesce/fuse the build material composition in contacttherewith while causing the 3D objects (or 3D objects regions) to bewhite or slightly colored. In these examples of the fusing agent, theenergy absorber is the plasmonic resonance absorber.

As used herein “absorption” means that at least 80% of radiation havingwavelengths within the specified range is absorbed. Also used herein,“transparency” means that 25% or less of radiation having wavelengthswithin the specified range is absorbed.

Core Fusing Agents

Some examples of the core fusing agent are dispersions including anenergy absorber (i.e., an active material). In some examples, the activematerial may be an infrared light absorbing colorant. In an example, theactive material is a near-infrared light absorber. Any near-infraredcolorants, e.g., those produced by Fabricolor, Eastman Kodak, or BASF,Yamamoto, may be used in the core fusing agent. As one example, the corefusing agent may be a printing liquid formulation including carbon blackas the active material. Examples of this printing liquid formulation arecommercially known as CM997A, 516458, C18928, C93848, C93808, or thelike, all of which are available from HP Inc.

As another example, the core fusing agent may be a printing liquidformulation including near-infrared absorbing dyes as the activematerial. Examples of this printing liquid formulation are described inU.S. Pat. No. 9,133,344, incorporated herein by reference in itsentirety. Some examples of the near-infrared absorbing dye arewater-soluble near-infrared absorbing dyes selected from the groupconsisting of:

and mixtures thereof. In the above formulations, M can be a divalentmetal atom (e.g., copper, etc.) or can have OSO₃Na axial groups fillingany unfilled valencies if the metal is more than divalent (e.g., indium,etc.), R can be hydrogen or any C₁-C₈ alkyl group (including substitutedalkyl and unsubstituted alkyl), and Z can be a counterion such that theoverall charge of the near-infrared absorbing dye is neutral. Forexample, the counterion can be sodium, lithium, potassium, NH₄ ⁺, etc.

Some other examples of the near-infrared absorbing dye are hydrophobicnear-infrared absorbing dyes selected from the group consisting of:

and mixtures thereof. For the hydrophobic near-infrared absorbing dyes,M can be a divalent metal atom (e.g., copper, etc.) or can include ametal that has CI, Br, or OR′ (R′═H, CH₃, COCH₃, COCH₂COOCH₃,COCH₂COCH₃) axial groups filling any unfilled valencies if the metal ismore than divalent, and R can be hydrogen or any C₁-C₈ alkyl group(including substituted alkyl and unsubstituted alkyl).

Other near-infrared absorbing dyes or pigments may be used. Someexamples include anthroquinone dyes or pigments, metal dithiolene dyesor pigments, cyanine dyes or pigments, perylenediimide dyes or pigments,croconium dyes or pigments, pyrilium or thiopyrilium dyes or pigments,boron-dipyrromethene dyes or pigments, or aza-boron-dipyrromethene dyesor pigments.

Anthroquinone dyes or pigments and metal (e.g., nickel) dithiolene dyesor pigments may have the following structures, respectively:

where R in the anthroquinone dyes or pigments may be hydrogen or anyC₁-C₈ alkyl group (including substituted alkyl and unsubstituted alkyl),and R in the dithiolene may be hydrogen, COOH, SO₃, NH₂, any C₁-C₈ alkylgroup (including substituted alkyl and unsubstituted alkyl), or thelike.

Cyanine dyes or pigments and perylenediimide dyes or pigments may havethe following structures, respectively:

where R in the perylenediimide dyes or pigments may be hydrogen or anyC₁-C₈ alkyl group (including substituted alkyl and unsubstituted alkyl).

Croconium dyes or pigments and pyrilium or thiopyrilium dyes or pigmentsmay have the following structures, respectively:

Boron-dipyrromethene dyes or pigments and aza-boron-dipyrromethene dyesor pigments may have the following structures, respectively:

The amount of the active material that is present in the core fusingagent ranges from greater than 0 wt % to about 40 wt % based on thetotal weight of the core fusing agent. In other examples, the amount ofthe active material in the core fusing agent ranges from about 0.3 wt %to 30 wt %, from about 1 wt % to about 20 wt %, from about 1.0 wt % upto about 10.0 wt %, or from greater than 4.0 wt % up to about 15.0 wt %.It is believed that these active material loadings provide a balancebetween the core fusing agent having jetting reliability and heat and/orradiation absorbance efficiency.

Primer Fusing Agents

Some examples of the primer fusing agent are dispersions including theplasmonic resonance absorber as the energy absorber. The absorption ofthe plasmonic resonance absorber is the result of the plasmonicresonance effects. Electrons associated with the atoms of the plasmonicresonance absorber may be collectively excited by radiation, whichresults in collective oscillation of the electrons. The wavelengths thatcan excite and oscillate these electrons collectively are dependent onthe number of electrons present in the plasmonic resonance absorberparticles, which in turn is dependent on the size of the plasmonicresonance absorber particles. The amount of energy that can collectivelyoscillate the particle's electrons is low enough that very smallparticles (e.g., 1-100 nm) may absorb radiation with wavelengths severaltimes (e.g., from 8 to 800 or more times) the size of the particles. Theuse of these particles allows the primer fusing agent to be inkjetjettable as well as electromagnetically selective (e.g., havingabsorption at wavelengths ranging from 800 nm to 4000 nm andtransparency at wavelengths ranging from 400 nm to 780 nm).

In an example, the plasmonic resonance absorber has an average particlediameter (e.g., volume-weighted mean diameter) ranging from greater than0 nm to less than 220 nm. In another example, the plasmonic resonanceabsorber has an average particle diameter ranging from greater than 0 nmto 120 nm. In a still another example, the plasmonic resonance absorberhas an average particle diameter ranging from about 10 nm to about 200nm.

In an example, the plasmonic resonance absorber is an inorganic pigment.Examples of suitable inorganic pigments include lanthanum hexaboride(LaB₆), tungsten bronzes (A_(x)WO₃), indium tin oxide (In₂O₃:SnO₂, ITO),antimony tin oxide (Sb₂O₃:SnO₂, ATO), titanium nitride (TiN), aluminumzinc oxide (AZO), ruthenium oxide (RuO₂), silver (Ag), gold (Au),platinum (Pt), iron pyroxenes (A_(x)Fe_(y)Si₂O₆ wherein A is Ca or Mg,x=1.5-1.9, and y=0.1-0.5), modified iron phosphates (A_(x)Fe_(y)PO₄),modified copper phosphates (A_(x)Cu_(y)PO_(z)), and modified copperpyrophosphates (A_(x)Cu_(y)P₂O₇). Tungsten bronzes may be alkali dopedtungsten oxides. Examples of suitable alkali dopants (i.e., A inA_(x)WO₃) may be cesium, sodium, potassium, or rubidium. In an example,the alkali doped tungsten oxide may be doped in an amount ranging fromgreater than 0 mol % to about 0.33 mol % based on the total mol % of thealkali doped tungsten oxide. Suitable modified iron phosphates(A_(x)Fe_(y)PO) may include copper iron phosphate (A=Cu, x=0.1-0.5, andy=0.5-0.9), magnesium iron phosphate (A=Mg, x=0.1-0.5, and y=0.5-0.9),and zinc iron phosphate (A=Zn, x=0.1-0.5, and y=0.5-0.9). For themodified iron phosphates, it is to be understood that the number ofphosphates may change based on the charge balance with the cations.Suitable modified copper pyrophosphates (A_(x)Cu_(y)P₂O₇) include ironcopper pyrophosphate (A=Fe, x=0-2, and y=0-2), magnesium copperpyrophosphate (A=Mg, x=0-2, and y=0-2), and zinc copper pyrophosphate(A=Zn, x=0-2, and y=0-2). Combinations of the inorganic pigments mayalso be used.

The amount of the plasmonic resonance absorber that is present in theprimer fusing agent ranges from greater than 0 wt % to about 40 wt %based on the total weight of the primer fusing agent. In other examples,the amount of the plasmonic resonance absorber in the primer fusingagent ranges from about 0.3 wt % to 30 wt %, from about 1 wt % to about20 wt %, from about 1.0 wt % up to about 10.0 wt %, or from greater than4.0 wt % up to about 15.0 wt %. It is believed that these plasmonicresonance absorber loadings provide a balance between the primer fusingagent having jetting reliability and heat and/or radiation absorbanceefficiency.

The plasmonic resonance absorber may, in some instances, be dispersedwith a dispersant. As such, the dispersant helps to uniformly distributethe plasmonic resonance absorber throughout the primer fusing agent.Examples of suitable dispersants include polymer or small moleculedispersants, charged groups attached to the plasmonic resonance absorbersurface, or other suitable dispersants. Some specific examples ofsuitable dispersants include a water-soluble acrylic acid polymer (e.g.,CARBOSPERSE® K7028 available from Lubrizol), water-solublestyrene-acrylic acid copolymers/resins (e.g., JONCRYL® 296, JONCRYL®671, JONCRYL® 678, JONCRYL® 680, JONCRYL® 683, JONCRYL® 690, etc.available from BASF Corp.), a high molecular weight block copolymer withpigment affinic groups (e.g., DISPERBYK®-190 available BYK Additives andInstruments), or water-soluble styrene-maleic anhydridecopolymers/resins.

Whether a single dispersant is used or a combination of dispersants isused, the total amount of dispersant(s) in the primer fusing agent mayrange from about 10 wt % to about 200 wt % based on the weight of theplasmonic resonance absorber in the primer fusing agent.

A silane coupling agent may also be added to the primer fusing agent tohelp bond the organic and inorganic materials. Examples of suitablesilane coupling agents include the SILQUEST® A series manufactured byMomentive.

Whether a single silane coupling agent is used or a combination ofsilane coupling agents is used, the total amount of silane couplingagent(s) in the primer fusing agent may range from about 0.1 wt % toabout 50 wt % based on the weight of the plasmonic resonance absorber inthe primer fusing agent. In an example, the total amount of silanecoupling agent(s) in the primer fusing agent ranges from about 1 wt % toabout 30 wt % based on the weight of the plasmonic resonance absorber.In another example, the total amount of silane coupling agent(s) in theprimer fusing agent ranges from about 2.5 wt % to about 25 wt % based onthe weight of the plasmonic resonance absorber.

One example of the primer fusing agent includes cesium tungsten oxide(CTO) nanoparticles as the plasmonic resonance absorber. The CTOnanoparticles have a formula of Cs_(x)WO₃, where 0<x<1. The cesiumtungsten oxide nanoparticles may give the primer fusing agent a lightblue color. The strength of the color may depend, at least in part, onthe amount of the CTO nanoparticles in the primer fusing agent. When itis desirable to form an outer white layer on the 3D object, less of theCTO nanoparticles may be used in the primer fusing agent in order toachieve the white color. In an example, the CTO nanoparticles may bepresent in the primer fusing agent in an amount ranging from about 1 wt% to about 20 wt % (based on the total weight of the primer fusingagent).

The average particle size (e.g., volume-weighted mean diameter) of theCTO nanoparticles may range from about 1 nm to about 40 nm. In someexamples, the average particle size of the CTO nanoparticles may rangefrom about 1 nm to about 15 nm or from about 1 nm to about 10 nm. Theupper end of the particle size range (e.g., from about 30 nm to about 40nm) may be less desirable, as these particles may be more difficult tostabilize.

This example of the primer fusing agent may also include a zwitterionicstabilizer. The zwitterionic stabilizer may improve the stabilization ofthis example of the primer fusing agent. While the zwitterionicstabilizer has an overall neutral charge, at least one area of themolecule has a positive charge (e.g., amino groups) and at least oneother area of the molecule has a negative charge. The CTO nanoparticlesmay have a slight negative charge. The zwitterionic stabilizer moleculesmay orient around the slightly negative CTO nanoparticles with thepositive area of the zwitterionic stabilizer molecules closest to theCTO nanoparticles and the negative area of the zwitterionic stabilizermolecules furthest away from the CTO nanoparticles. Then, the negativecharge of the negative area of the zwitterionic stabilizer molecules mayrepel CTO nanoparticles from each other. The zwitterionic stabilizermolecules may form a protective layer around the CTO nanoparticles, andprevent them from coming into direct contact with each other and/orincrease the distance between the particle surfaces (e.g., by a distanceranging from about 1 nm to about 2 nm). Thus, the zwitterionicstabilizer may prevent the CTO nanoparticles from agglomerating and/orsettling in the primer fusing agent.

Examples of suitable zwitterionic stabilizers include C₂ to C₈ betaines,C₂ to C₈ aminocarboxylic acids having a solubility of at least 10 g in100 g of water, taurine, and combinations thereof. Examples of the C₂ toC₈ aminocarboxylic acids include beta-alanine, gamma-aminobutyric acid,glycine, and combinations thereof.

The zwitterionic stabilizer may be present in the primer fusing agent inan amount ranging from about 2 wt % to about 35 wt % (based on the totalweight of the primer fusing agent). When the zwitterionic stabilizer isthe C₂ to C₈ betaine, the C₂ to C₈ betaine may be present in an amountranging from about 8 wt % to about 35 wt % of the total weight of theprimer fusing agent. When the zwitterionic stabilizer is the C₂ to C₈aminocarboxylic acid, the C₂ to C₈ aminocarboxylic acid may be presentin an amount ranging from about 2 wt % to about 20 wt % of the totalweight of the primer fusing agent. When the zwitterionic stabilizer istaurine, taurine may be present in an amount ranging from about 2 wt %to about 35 wt % of the total weight of the primer fusing agent.

In this example, the weight ratio of the CTO nanoparticles to thezwitterionic stabilizer may range from 1:10 to 10:1; or the weight ratioof the CTO nanoparticles to the zwitterionic stabilizer may be 1:1.

Fusing Agent Vehicles

As used herein, “FA vehicle” may refer to the liquid in which the energyabsorber (e.g., the active material or the plasmonic resonance absorber)is dispersed or dissolved to form the fusing agent (e.g., the corefusing agent or the primer fusing agent). A wide variety of FA vehicles,including aqueous and non-aqueous vehicles, may be used in the fusingagent. In some examples, the FA vehicle may include water alone or anon-aqueous solvent alone with no other components. In other examples,the FA vehicle may include other components, depending, in part, uponthe applicator that is to be used to dispense the fusing agent. Examplesof other suitable fusing agent components include co-solvent(s),humectant(s), surfactant(s), antimicrobial agent(s), anti-kogationagent(s), and/or chelating agent(s).

The solvent of the fusing agent may be water or a non-aqueous solvent(e.g., ethanol, acetone, n-methyl pyrrolidone, aliphatic hydrocarbons,etc.). In some examples, the fusing agent consists of the energyabsorber and the solvent (without other components). In these examples,the solvent makes up the balance of the fusing agent.

Classes of organic co-solvents that may be used in a water-based fusingagent include aliphatic alcohols, aromatic alcohols, diols, glycolethers, polyglycol ethers, 2-pyrrolidones, caprolactams, formamides,acetamides, glycols, and long chain alcohols. Examples of theseco-solvents include primary aliphatic alcohols, secondary aliphaticalcohols, 1,2-alcohols, 1,3-alcohols, 1,5-alcohols, 1,6-hexanediol orother diols (e.g., 1,5-pentanediol, 2-methyl-1,3-propanediol, etc.),ethylene glycol alkyl ethers, propylene glycol alkyl ethers, higherhomologs (C₆-C₁₂) of polyethylene glycol alkyl ethers, triethyleneglycol, tetraethylene glycol, tripropylene glycol methyl ether, N-alkylcaprolactams, unsubstituted caprolactams, both substituted andunsubstituted formamides, both substituted and unsubstituted acetamides,and the like. Other examples of organic co-solvents include dimethylsulfoxide (DMSO), isopropyl alcohol, ethanol, pentanol, acetone, or thelike.

Other examples of suitable co-solvents include water-solublehigh-boiling point solvents, which have a boiling point of at least 120°C., or higher. Some examples of high-boiling point solvents include2-pyrrolidone (i.e., 2-pyrrolidinone, boiling point of about 245° C.),1-methyl-2-pyrrolidone (boiling point of about 203° C.),N-(2-hydroxyethyl)-2-pyrrolidone (boiling point of about 140° C.),2-methyl-1,3-propanediol (boiling point of about 212° C.), andcombinations thereof.

The co-solvent(s) may be present in the fusing agent in a total amountranging from about 1 wt % to about 50 wt % based upon the total weightof the fusing agent, depending upon the jetting architecture of theapplicator. In an example, the total amount of the co-solvent(s) presentin the fusing agent is 25 wt % based on the total weight of the fusingagent.

The co-solvent(s) of the fusing agent may depend, in part, upon thejetting technology that is to be used to dispense the fusing agent. Forexample, if thermal inkjet printheads are to be used, water and/orethanol and/or other longer chain alcohols (e.g., pentanol) may be thesolvent (i.e., makes up 35 wt % or more of the fusing agent) orco-solvents. For another example, if piezoelectric inkjet printheads areto be used, water may make up from about 25 wt % to about 30 wt % of thefusing agent, and the solvent (i.e., 35 wt % or more of the fusingagent) may be ethanol, isopropanol, acetone, etc. The co-solvent(s) ofthe fusing agent may also depend, in part, upon the build materialcomposition that is being used with the fusing agent. For a hydrophobicpowder (such as a polyether block amide polymer including more polyamideblocks than polyether blocks, a polyether block amide polymer where thepolyamide blocks are larger than the polyether blocks, a polyether blockamide polymer where the polyether blocks are relatively hydrophobic,etc.), the FA vehicle may include a higher solvent content in order toimprove the flow of the fusing agent into the build materialcomposition.

The FA vehicle may also include humectant(s). In an example, the totalamount of the humectant(s) present in the fusing agent ranges from about3 wt % to about 10 wt %, based on the total weight of the fusing agent.An example of a suitable humectant is ethoxylated glycerin having thefollowing formula:

in which the total of a+b+c ranges from about 5 to about 60, or in otherexamples, from about 20 to about 30. An example of the ethoxylatedglycerin is LIPON IC® EG-1 (LEG-1, glycereth-26, a+b+c=26, availablefrom Lipo Chemicals).

In some examples, the FA vehicle includes surfactant(s) to improve thejettability of the fusing agent. Examples of suitable surfactantsinclude a self-emulsifiable, non-ionic wetting agent based on acetylenicdiol chemistry (e.g., SURFYNOL® SEF from Air Products and Chemicals,Inc.), a non-ionic fluorosurfactant (e.g., CAPSTONE® fluorosurfactants,such as CAPSTONE® FS-35, from Chemours), and combinations thereof. Inother examples, the surfactant is an ethoxylated low-foam wetting agent(e.g., SURFYNOL® 440 or SURFYNOL® CT-111 from Air Products and ChemicalInc.) or an ethoxylated wetting agent and molecular defoamer (e.g.,SURFYNOL® 420 from Air Products and Chemical Inc.). Still other suitablesurfactants include non-ionic wetting agents and molecular defoamers(e.g., SURFYNOL® 104E from Air Products and Chemical Inc.) orwater-soluble, non-ionic surfactants (e.g., TERGITOL™ TMN-6, TERGITOL™15-S-7, or TERGITOL™ 15-S-9 (a secondary alcohol ethoxylate) from TheDow Chemical Company or TECO® Wet 510 (polyether siloxane) availablefrom Evonik Industries).

Whether a single surfactant is used or a combination of surfactants isused, the total amount of surfactant(s) in the fusing agent may rangefrom about 0.01 wt % to about 10 wt % based on the total weight of thefusing agent. In an example, the total amount of surfactant(s) in thefusing agent may be about 3 wt % based on the total weight of the fusingagent.

An anti-kogation agent may be included in the fusing agent that is to bejetted using thermal inkjet printing. Kogation refers to the deposit ofdried printing liquid (e.g., fusing agent) on a heating element of athermal inkjet printhead. Anti-kogation agent(s) is/are included toassist in preventing the buildup of kogation. Examples of suitableanti-kogation agents include oleth-3-phosphate (e.g., commerciallyavailable as CRODAFOS™ 03 A or CRODAFOS™ N-3 acid from Croda), or acombination of oleth-3-phosphate and a low molecular weight (e.g.,<5,000) polyacrylic acid polymer (e.g., commercially available asCARBOSPERSE™ K-7028 Polyacrylate from Lubrizol).

Whether a single anti-kogation agent is used or a combination ofanti-kogation agents is used, the total amount of anti-kogation agent(s)in the fusing agent may range from greater than 0.20 wt % to about 0.65wt % based on the total weight of the fusing agent. In an example, theoleth-3-phosphate is included in an amount ranging from about 0.20 wt %to about 0.60 wt %, and the low molecular weight polyacrylic acidpolymer is included in an amount ranging from about 0.005 wt % to about0.03 wt %.

The FA vehicle may also include antimicrobial agent(s). Suitableantimicrobial agents include biocides and fungicides. Exampleantimicrobial agents may include the NUOSEPT™ (Troy Corp.), UCARCIDE™(Dow Chemical Co.), ACTICIDE® B20 (Thor Chemicals), ACTICIDE® M20 (ThorChemicals), ACTICIDE® MBL (blends of 2-methyl-4-isothiazolin-3-one(MIT), 1,2-benzisothiazolin-3-one (BIT) and Bronopol) (Thor Chemicals),AXIDE™ (Planet Chemical), NIPACIDE™ (Clariant), blends of5-chloro-2-methyl-4-isothiazolin-3-one (CIT or CMIT) and MIT under thetradename KATHON™ (Dow Chemical Co.), and combinations thereof. Examplesof suitable biocides include an aqueous solution of1,2-benzisothiazolin-3-one (e.g., PROXEL® GXL from Arch Chemicals,Inc.), quaternary ammonium compounds (e.g., BARDAC® 2250 and 2280,BARQUAT® 50-65B, and CARBOQUAT® 250-T, all from Lonza Ltd. Corp.), andan aqueous solution of methylisothiazolone (e.g., KORDEK® MLX from DowChemical Co.).

In an example, the fusing agent may include a total amount ofantimicrobial agents that ranges from about 0.05 wt % to about 1 wt %.In an example, the antimicrobial agent(s) is/are a biocide(s) and is/arepresent in the fusing agent in an amount of about 0.25 wt % (based onthe total weight of the fusing agent).

Chelating agents (or sequestering agents) may be included in the FAvehicle to eliminate the deleterious effects of heavy metal impurities.Examples of chelating agents include disodium ethylenediaminetetraaceticacid (EDTA-Na), ethylene diamine tetra acetic acid (EDTA), andmethylglycinediacetic acid (e.g., TRILON® M from BASF Corp.).

Whether a single chelating agent is used or a combination of chelatingagents is used, the total amount of chelating agent(s) in the fusingagent may range from greater than 0 wt % to about 2 wt % based on thetotal weight of the fusing agent. In an example, the chelating agent(s)is/are present in the fusing agent in an amount of about 0.04 wt %(based on the total weight of the fusing agent).

Coloring Agents

In the examples of the 3D printing kit, the 3D printing methods, and the3D printing system disclosed herein, a coloring agent may be used. Thecoloring agent may include a colorant, a co-solvent, and a balance ofwater. In some examples, the coloring agent consists of thesecomponents, and no other components. In some other examples, thecoloring agent may further include a binder (e.g., an acrylic latexbinder, which may be a copolymer of any two or more of styrene, acrylicacid, methacrylic acid, methyl methacrylate, ethyl methacrylate, andbutyl methacrylate) and/or a buffer. In still other examples, thecoloring agent may further include additional components, such asdispersant(s), humectant(s), surfactant(s), anti-kogation agent(s),antimicrobial agent(s), and/or chelating agent(s) (each of which isdescribed above in reference to the fusing agent).

The coloring agent may be a black agent, a cyan agent, a magenta agent,or a yellow agent. As such, the colorant may be a black colorant, a cyancolorant, a magenta colorant, a yellow colorant, or a combination ofcolorants that together achieve a black, cyan, magenta, or yellow color.

In some instances, the colorant of the coloring agent may be transparentto infrared wavelengths. In other instances, the colorant of thecoloring agent may not be completely transparent to infraredwavelengths, but does not absorb enough radiation to sufficiently heatthe build material composition in contact therewith. In an example, thecolorant absorbs less than 10% of radiation having wavelengths in arange of 650 nm to 2500 nm. In another example, the colorant absorbsless than 20% of radiation having wavelengths in a range of 650 nm to4000 nm.

The colorant of the coloring agent is also capable of absorbingradiation with wavelengths of 650 nm or less. As such, the colorantabsorbs at least some wavelengths within the visible spectrum, butabsorbs little or no wavelengths within the near-infrared spectrum. Thisis in contrast to at least some examples of the energy absorber in thefusing agent, which absorbs wavelengths within the near-infraredspectrum and/or the infrared spectrum (e.g., the fusing agent absorbs80% or more of radiation with wavelengths within the near-infraredspectrum and/or the infrared spectrum). As such, the colorant in thecoloring agent will not substantially absorb the fusing radiation, andthus will not initiate coalescing/fusing of the build materialcomposition in contact therewith when the build material composition isexposed to the fusing radiation.

Examples of IR transparent colorants include acid yellow 23 (AY 23),AY17, acid red 52 (AR 52), AR 289, and reactive red 180 (RR 180).Examples of colorants that absorb some visible wavelengths and some IRwavelengths include cyan colorants, such as direct blue 199 (DB 199) andpigment blue 15:3 (PB 15:3).

In other examples, the colorant may be any azo dye having sodium orpotassium counter ion(s) or any diazo (i.e., double azo) dye havingsodium or potassium counter ion(s).

Examples of black dyes may include tetrasodium(6Z)-4-acetamido-5-oxo-6-[[7-sulfonato-4-(4-sulfonatophenyl)azo-1-naphthyl]hydrazono]naphthalene-1,7-disulfonatewith a chemical structure of:

(commercially available as Food Black 1); tetrasodium6-amino-4-hydroxy-3-[[7-sulfonato-4-[(4-sulfonatophenyl)azo]-1-naphthyl]azo]naphthalene-2,7-disulfonatewith a chemical structure of:

(commercially available as Food Black 2); tetrasodium(6E)-4-amino-5-oxo-3-[[4-(2-sulfonatooxyethylsulfonyl)phenyl]diazenyl]-6-[[4-(2-sulfonatooxyethylsulfonyl)phenyl]hydrazinylidene]naphthalene-2,7-disulfonatewith a chemical structure of:

(commercially available as Reactive Black 31); tetrasodium(6E)-4-amino-5-oxo-3-[[4-(2-sulfonatooxyethylsulfonyl)phenyl]diazenyl]-6-[[4-(2-sulfonatooxyethylsulfonyl)phenyl]hydrazinylidene]naphthalene-2,7-disulfonatewith a chemical structure of:

and combinations thereof. Some other commercially available examples ofblack dyes include multipurpose black azo-dye based liquids, such asPRO-JET® Fast Black 1 (made available by Fujifilm Holdings), and blackazo-dye based liquids with enhanced water fastness, such as PRO-JET®Fast Black 2 (made available by Fujifilm Holdings).

Examples of cyan dyes include ethyl-[4-[[4-[ethyl-[(3-sulfophenyl)methyl] amino] phenyl]-(2-sulfophenyl)ethylidene]-1-cyclohexa-2,5-dienylidene]-[(3-sulfophenyl) methyl]azanium with a chemical structure of:

(commercially available as Acid Blue 9, where the counter ion mayalternatively be sodium counter ions or potassium counter ions); sodium4-[(E)-{4-[benzyl(ethyl)amino]phenyl}{(4E)-4-[benzyl(ethyl)iminio]cyclohexa-2,5-dien-1-ylidene}methyl]benzene-1,3-disulfonatewith a chemical structure of:

(commercially available as Acid Blue 7); and a phthalocyanine with achemical structure of:

(commercially available as Direct Blue 199); and combinations thereof.

An example of the pigment based coloring agent may include from about 1wt % to about 10 wt % of pigment(s), from about 10 wt % to about 30 wt %of co-solvent(s), from about 1 wt % to about 10 wt % of dispersant(s),from about 0.1 wt % to about 5 wt % of binder(s), from 0.01 wt % toabout 1 wt % of anti-kogation agent(s), from about 0.05 wt % to about0.1 wt % antimicrobial agent(s), and a balance of water. An example ofthe dye based coloring agent may include from about 1 wt % to about 7 wt% of dye(s), from about 10 wt % to about 30 wt % of co-solvent(s), fromabout 1 wt % to about 7 wt % of dispersant(s), from about 0.05 wt % toabout 0.1 wt % antimicrobial agent(s), from 0.05 wt % to about 0.1 wt %of chelating agent(s), from about 0.005 wt % to about 0.2 wt % ofbuffer(s), and a balance of water.

Some examples of the coloring agent include a set of cyan, magenta, andyellow agents, such as C1893A (cyan), C1984A (magenta), and C1985A(yellow); or C4801A (cyan), C4802A (magenta), and C4803A (yellow); allof which are available from HP Inc. Other commercially availablecoloring agents include C9384A (printhead HP 72), C9383A (printhead HP72), C4901A (printhead HP 940), and C4900A (printhead HP 940).

Detailing Agents

In the examples of the 3D printing kit, the 3D printing methods, and the3D printing system disclosed herein a detailing agent may be used. Thedetailing agent may include a surfactant, a co-solvent, and a balance ofwater. In some examples, the detailing agent consists of thesecomponents, and no other components. In some other examples, thedetailing agent may further include additional components, such ashumectant(s), anti-kogation agent(s), antimicrobial agent(s), and/orchelating agent(s) (each of which is described above in reference to thefusing agent).

The surfactant(s) that may be used in the detailing agent include any ofthe surfactants listed above in reference to the fusing agent. The totalamount of surfactant(s) in the detailing agent may range from about 0.10wt % to about 5.00 wt % with respect to the total weight of thedetailing agent.

The co-solvent(s) that may be used in the detailing agent include any ofthe co-solvents listed above in reference to the fusing agent. The totalamount of co-solvent(s) in the detailing agent may range from about 1.00wt % to about 20.00 wt % with respect to the total weight of thedetailing agent.

Similar to the fusing agent, the co-solvent(s) of the detailing agentmay depend, in part upon the jetting technology that is to be used todispense the detailing agent. For example, if thermal inkjet printheadsare to be used, water and/or ethanol and/or other longer chain alcohols(e.g., pentanol) may make up 35 wt % or more of the detailing agent. Foranother example, if piezoelectric inkjet printheads are to be used,water may make up from about 25 wt % to about 30 wt % of the detailingagent, and 35 wt % or more of the detailing agent may be ethanol,isopropanol, acetone, etc.

The balance of the detailing agent is water. As such, the amount ofwater may vary depending upon the amounts of the other components thatare included.

While the example detailing agent described herein does not include acolorant, it is to be understood that any of the colorants described forthe coloring agent (i.e., transparent to infrared wavelengths) may beused in the detailing agent. As one example, it may be desirable to addcolor to the detailing agent when the detailing agent is applied to theedge of a colored part. Color in the detailing agent may be desirablewhen used at a part edge because some of the colorant may becomeembedded in the build material that fuses/coalesces at the edge.

Printing Methods and Methods of Use

Referring now to FIGS. 1 and 2, examples of a method 100 for using the3D printing kit and a method 200 for 3D printing are depicted. Theexamples of the methods 100, 200 may use examples of the 3D printing kitand/or composition disclosed herein. Additionally, the examples of themethods 100, 200 may be used to print 3D objects that exhibit a whitecolor, a cyan color, a magenta color, a yellow color, a black color, ora combination thereof.

As shown in FIG. 1, the method 100 for using the three-dimensional (3D)printing kit comprises: applying a build material composition to form abuild material layer, the build material composition including athermoplastic elastomer having: an avalanche angle ranging from about 49degrees to about 59 degrees; a break energy ranging from about 55 kJ/kgto about 78 kJ/kg; and an avalanche energy ranging from about 10 kJ/kgto about 27 kJ/kg (reference numeral 102); based on a 3D object model,selectively applying a fusing agent on at least a portion of the buildmaterial layer (reference numeral 104); and exposing the build materiallayer to electromagnetic radiation to coalesce the build materialcomposition in the at least the portion to form a layer of a 3D object(reference numeral 106).

In some examples, the method 100 further comprises: iteratively applyingindividual build material layers of the build material composition;based on the 3D object model, selectively applying the fusing agent toat least some of the individual build material layers to defineindividually patterned layers, wherein the fusing agent is selected fromthe group consisting of a core fusing agent, a primer fusing agent, orboth the core fusing agent and the primer fusing agent; and iterativelyexposing the individually patterned layers to the electromagneticradiation to form individual object layers, wherein each of theindividual object layers is selected from the group consisting of a corelayer, a primer layer, or a layer including a core portion and a primerportion.

In some examples of the method 100, the fusing agent is a core fusingagent; exposing the layer to electromagnetic radiation forms a corelayer; and the method 100 further comprises applying a second layer ofthe build material composition on the core layer; based on the 3D objectmodel, selectively applying a primer fusing agent on at least a portionof the second layer, the primer fusing agent including a plasmonicresonance absorber having absorption at wavelengths ranging from 800 nmto 4000 nm and having transparency at wavelengths ranging from 400 nm to780 nm; and exposing the second layer to electromagnetic radiation tofuse the build material composition in the at least the portion of thesecond layer to form a primer layer. This example of the method 100 mayfurther include applying a third layer of the build material compositionon the primer layer; based on the 3D object model, selectively applyinga coloring agent and (i) the core fusing agent or (ii) the primer fusingagent on at least a portion of the third layer; and exposing the thirdlayer to electromagnetic radiation to fuse the build materialcomposition in the at least the portion of the third layer to form acolored layer having a colorant of the coloring agent embedded therein.

As shown in FIG. 2, the method 200 for three-dimensional (3D) printingcomprises: based on a 3D object model, selectively applying a corefusing agent on at least a portion of a first layer of a build materialcomposition, the build material composition including a thermoplasticelastomer having: an avalanche angle ranging from about 49 degrees toabout 59 degrees; a break energy ranging from about 55 kJ/kg to about 78kJ/kg; and an avalanche energy ranging from about 10 kJ/kg to about 27kJ/kg (reference numeral 202); exposing the first layer toelectromagnetic radiation to fuse the build material composition in theat least the portion of the first layer to form a core layer (referencenumeral 204); applying a second layer of the build material compositionon the core layer (reference numeral 206); based on the 3D object model,selectively applying a primer fusing agent on at least a portion of thesecond layer, the primer fusing agent including a plasmonic resonanceabsorber having absorption at wavelengths ranging from 800 nm to 4000 nmand having transparency at wavelengths ranging from 400 nm to 780 nm(reference numeral 208); and exposing the second layer toelectromagnetic radiation to fuse the build material composition in theat least the portion of the second layer to form a primer layer(reference numeral 210).

In some examples, the method 200 further comprises: applying a thirdlayer of the build material composition on the primer layer; based onthe 3D object model, selectively applying a coloring agent and (i) thecore fusing agent or (ii) the primer fusing agent on at least a portionof the third layer; and exposing the third layer to electromagneticradiation to fuse the build material composition in the at least theportion of the third layer to form a colored layer having a colorant ofthe coloring agent embedded therein.

The methods 100, 200 may be used to form an object 44 as shown in FIG.3, which includes several core layers 46, 46′, 46″ and an outer whitelayer 48 (also referred to herein as a primer layer). The core layers46, 46′, 46″ are sequentially formed by selectively patterningrespective build material layers with the core fusing agent 28 andexposing each patterned layer to electromagnetic radiation. The corelayers 46, 46′, 46″ may be black or a dark color due to the absorber inthe core fusing agent 28. The outer white layer 48 is formed by applyinga build material layer on the outermost core layer 46″, patterning itwith the primer fusing agent 26, 26′, and exposing it to electromagneticradiation. Since the primer fusing agent 26, 26′ has no or low tint, thewhite color of the build material composition 16 is visible, and thusgives the outer white layer 48 its white appearance. The outer whitelayer 48 provides the object 44 with a white (or slightly tinted)exterior surface. As such, the outer white layer 48 optically isolatesthe black core layer(s) 46, 46′, 46″ that it covers.

In the example object 44 shown in FIG. 3, the outer white layer 48 doesnot completely surround the object 44, but rather may be formed on theouter surface(s) of the core layer 46″ that will be visible. Forexample, in FIG. 3, the surface 50 of the object 44 may not be visiblewhen the object 44 is in use, and thus it may not be desirable to formthe outer white layer 48 on this surface 50.

It is to be understood that the methods 100, 200 may include additionalprocessing to form the object 44 with an outer colored layer (not shownin FIG. 3) on at least a portion of the outer white layer 48, or to formanother object 44′ (shown in FIG. 4H) which has the core layer(s) 46completely encapsulated by a primer layer (including primer layerportions 48′, 48″, 48′″, which are referred to herein respectively asprimer layers 48, 48′, 48″) and an outer colored layer (includingcolored layer portions 52, 52′, 52″, which are referred to herein ascolored layers 52, 52′, 52″).

The method 300 to form the object 44′ will now be discussed in referenceto FIGS. 4A through 4H. It is to be understood that the method 300 maybe an example of the method 100 and/or the method 200.

Prior to execution of any of the methods 100, 200, 300 disclosed hereinor as part of the methods 100, 200, 300 a controller 36 (see, e.g., FIG.7) may access data stored in a data store 34 (see, e.g., FIG. 7)pertaining to a 3D object 44′ that is to be printed. For example, thecontroller 36 may determine the number of layers of the build materialcomposition 16 that are to be formed, the locations at which the fusingagent(s) 26, 26′, 28 from the applicator(s) 24A, 24B is/are to bedeposited on each of the respective layers, etc.

In FIGS. 4A and 4B, a layer 54 of the build material composition 16 isapplied on the build area platform 12. As mentioned above, the buildmaterial composition 16 includes at least the thermoplastic elastomer,and may additionally include the antioxidant, the whitener, theantistatic agent, the flow aid, or combinations thereof.

In the example shown in FIGS. 4A and 4B, a printing system (e.g., theprinting system 10 shown in FIG. 7) may be used to apply the buildmaterial composition 16. The printing system 10 may include a build areaplatform 12, a build material supply 14 containing the build materialcomposition 16, and a build material distributor 18.

The build area platform 12 receives the build material composition 16from the build material supply 14. The build area platform 12 may bemoved in the directions as denoted by the arrow 20 (see FIG. 7), e.g.,along the z-axis, so that the build material composition 16 may bedelivered to the build area platform 12 or to a previously formed layer.In an example, when the build material composition 16 is to bedelivered, the build area platform 12 may be programmed to advance(e.g., downward) enough so that the build material distributor 18 canpush the build material composition 16 onto the build area platform 12to form a substantially uniform layer of the build material composition16 thereon. The build area platform 12 may also be returned to itsoriginal position, for example, when a new part is to be built.

The build material supply 14 may be a container, bed, or other surfacethat is to position the build material composition 16 between the buildmaterial distributor 18 and the build area platform 12. In someexamples, the methods 100, 200, 300 further include heating the buildmaterial composition 16 in the build material supply 14 to a supplytemperature ranging from about 40° C. to about 100° C. In theseexamples, the supply temperature may depend, in part, on the buildmaterial composition 16 used and/or the 3D printer used. The heating ofthe build material composition 16 in the build material supply 14 may beaccomplished by heating the build material supply 14 to the supplytemperature.

The build material distributor 18 may be moved in the directions asdenoted by the arrow 22 (see FIG. 7), e.g., along the y-axis, over thebuild material supply 14 and across the build area platform 12 to spreadthe layer 54 of the build material composition 16 over the build areaplatform 12. The build material distributor 18 may also be returned to aposition adjacent to the build material supply 14 following thespreading of the build material composition 16. The build materialdistributor 18 may be a blade (e.g., a doctor blade), a roller, acombination of a roller and a blade, and/or any other device capable ofspreading the build material composition 16 over the build area platform12. For instance, the build material distributor 18 may be acounter-rotating roller. In some examples, the build material supply 14or a portion of the build material supply 14 may translate along withthe build material distributor 18 such that build material composition16 is delivered continuously to the material distributor 18 rather thanbeing supplied from a single location at the side of the printing system10 as depicted in FIG. 4A.

In FIG. 4A, the build material supply 14 may supply the build materialcomposition 16 into a position so that it is ready to be spread onto thebuild area platform 12. The build material distributor 18 may spread thesupplied build material composition 16 onto the build area platform 12.The controller 34 may process “control build material supply” data, andin response, control the build material supply 14 to appropriatelyposition the particles of the build material composition 16, and mayprocess “control spreader” data, and in response, control the buildmaterial distributor 18 to spread the supplied build materialcomposition 16 over the build area platform 12 to form the layer 54 ofbuild material composition 16 thereon. As shown in FIG. 4B, one buildmaterial layer 54 has been formed.

The layer 54 of the build material composition 16 has a substantiallyuniform thickness across the build area platform 12. In an example, thebuild material layer 54 has a thickness ranging from about 50 μm toabout 120 μm. In another example, the thickness of the build materiallayer 54 ranges from about 30 μm to about 300 μm. It is to be understoodthat thinner or thicker layers may also be used. For example, thethickness of the build material layer 54 may range from about 20 μm toabout 500 μm. The layer thickness may be about 2× (i.e., 2 times) theaverage diameter of the build material composition particles at aminimum for finer part definition. In some examples, the layer thicknessmay be about 1.2x the average diameter of the build material compositionparticles.

To form the object 44 shown in FIG. 3, this layer 54 of build materialcomposition 16 would be patterned with the core fusing agent 28 (i.e.,the core fusing agent 28 would be selectively dispensed on the layer 54according to a pattern of a cross-section for the core layer 46), andthen exposed to electromagnetic radiation to form the core layer 46. Asused herein, the cross-section of the layer of the part to be formedrefers to the cross-section that is parallel to the contact surface ofthe build area platform 12. As an example, if the core layer 46 is to beshaped like a cube or cylinder, the core fusing agent 28 will bedeposited in a square pattern or a circular pattern (from a top view),respectively, on at least a portion of the layer 54 of the buildmaterial composition 16.

In the example shown in FIG. 4B, the layer 54 of build materialcomposition 16 is a sacrificial layer that is used to enhance the colorof the first layer (e.g., colored layer 52) of the object 44′ that isbeing formed. As shown in FIG. 4B, the coloring agent 30 is selectivelyapplied to at least the portion 56 of the layer 54. As such, theparticles of the build material composition 16 in this portion 56 of thelayer 54 become colored. In this example, this sacrificial layer 54 isnot coalesced/fused (as no primer fusing agent 26, 26′ or core fusingagent 28 is applied thereon). Rather, some of the colored particle ofthe build material composition 16 in the sacrificial layer 54 may becomeembedded in coalesced/fused build material composition of the part layer(e.g., colored layer 52) that is formed thereon. In other words, some ofthe colored build material composition 16 in portion 56 may becomeembedded in the surface of the part layer that is formed adjacentthereto. The non-coalesced/non-fused, but embedded colored buildmaterial composition 16 may help to maintain saturation at the surface(of the ultimately formed colored layer 52) by providing a coloredinterface between the colored layer 52 and surroundingnon-coalesced/non-fused build material composition 16.

It is to be understood that the selective application of the coloringagent 30 may be accomplished in a single printing pass or in multipleprinting passes. In an example, selectively applying of the coloringagent 30 is accomplished in multiple printing passes. In anotherexample, the selectively applying of the coloring agent 30 isaccomplished in a number of printing passes ranging from 2 to 4. It maybe desirable to apply the coloring agent 30 in multiple printing passesto increase the amount of the colorant that is applied to the buildmaterial composition 16, to avoid liquid splashing, to avoiddisplacement of the build material composition 16, etc.

It is also to be understood that when an agent (e.g., the primer fusingagent 26, 26′, the core fusing agent 28, the coloring agent 30, thedetailing agent 42, etc.) is to be selectively applied to the buildmaterial composition 16, the agent 26, 26′, 28, 30, 42 may be dispensedfrom an applicator 24A, 24B, 24C. The applicator(s) 24A, 24B, 24C mayeach be a thermal inkjet printhead, a piezoelectric printhead, acontinuous inkjet printhead, etc., and the selective application of theagent(s) 26, 26′, 28, 30, 42 may be accomplished by thermal inkjetprinting, piezo electric inkjet printing, continuous inkjet printing,etc. The controller 36 may process data, and in response, control theapplicator(s) 24A, 24B, 24C (e.g., in the directions indicated by thearrow 32, see FIG. 7) to deposit the agent(s) 26, 26′, 28, 30, 42 ontopredetermined portion(s) of the build material composition 16.Throughout the method 300, a single applicator may be labeled withmultiple reference numbers (24A, 24B and/or 24C), although it is to beunderstood that the applicators may be separate applicators or a singleapplicator with several individual cartridges for dispensing therespective agents 26, 26′, 28, 30, 42.

While not shown in FIG. 4B, the detailing agent 42 may be selectivelyapplied on the portion 56 with the coloring agent 30. The detailingagent 42 may be used to maintain the temperature of the build materialcomposition 16 in contact therewith below the lowest temperature in themelting range of the thermoplastic elastomer of the build materialcomposition 16. Since the sacrificial layer 54 is not to becoalesced/fused, the detailing agent 42 may be applied to this layer 54with the coloring agent 30.

Additionally, while one sacrificial layer 54 is shown, it is to beunderstood that several sacrificial layers 54 may be sequentially formedin contact with one another.

The color of the coloring agent 30 that is applied to the portion(s) 56of the sacrificial layer 54 will depend upon the desired color for theobject 44′ or at least the portion of the colored layer 52 formedadjacent thereto. As examples, a black agent, a cyan agent, a magentaagent, or a yellow agent may be applied alone or in combination toachieve a variety of colors.

The coloring agent 30 will penetrate at least partially into thesacrificial layer 54. Depending upon the particle size of the colorantin the coloring agent 30 and size of the voids between the particles ofthe build material composition 16, the coloring agent 30 may penetratethroughout the entire thickness of the sacrificial layer 54. Thiscreates a surface upon which a subsequent layer 58 of build materialcomposition 16 may be applied.

The layer 58 of the build material composition 16 may be applied in thesame manner as the layer 54. The layer 58 is shown in FIG. 4C. The layer58 may be considered to be the first build material layer because atleast a portion of this layer 58 will be coalesced/fused to form thefirst layer of the 3D object 44′ (since the sacrificial layer 54 is notcoalesced/fused).

After the build material composition 16 has been applied, and prior tofurther processing, the build material layer 58 may be exposed toheating. Heating may be performed to pre-heat the build materialcomposition 16, and thus the heating temperature may be below the lowesttemperature in the melting range of the thermoplastic elastomer of thebuild material composition 16. As such, the temperature selected willdepend upon the build material composition 16 that is used. As examples,the pre-heating temperature may be from about 5° C. to about 50° C.below the lowest temperature in the melting range of the thermoplasticelastomer. In an example, the pre-heating temperature ranges from about50° C. to about 125° C. In another example, the pre-heating temperatureranges from about 80° C. to about 110° C. In still another example, thepre-heating temperature ranges from about 70° C. to about 105° C. In yetanother example, the methods 100, 200, 300 further include, prior to theselectively applying of the fusing agent 26, 26′, 28, pre-heating thebuild material composition 16 to a pre-heating temperature ranging fromabout 5° C. to about 50° C. below the lowest temperature in the meltingrange of the thermoplastic elastomer. The low pre-heating temperaturemay enable the non-patterned build material composition 16 to be easilyremoved from the 3D object 44′ after completion of the 3D object 44′.

Pre-heating the layer 58 of the build material composition 16 may beaccomplished by using any suitable heat source that exposes all of thebuild material composition 16 on in the layer 58 to the heat. Examplesof the heat source include a thermal heat source (e.g., a heater (notshown) integrated into the build area platform 12 (which may includesidewalls)) or the radiation source 38, 38′ (see, e.g., FIG. 7).

After the layer 58 is formed, and in some instances is pre-heated, theprimer fusing agent 26, 26′ and the coloring agent 30 are selectivelyapplied on the same portion(s) 60 of the build material composition 16in the layer 58.

As mentioned above, the primer fusing agent 26, 26′ includes an aqueousor non-aqueous vehicle and a plasmonic resonance absorber dispersedtherein. The fusing agent 26′ is one specific example of the low tint orprimer fusing agent, which includes CTO nanoparticles as the plasmonicresonance absorber, a zwitterionic stabilizer, and an aqueous vehicle.Example compositions of the primer fusing agent 26, 26′ are describedabove.

When the desired color for the object 44′ or a particular colored layer52 of the object 44′ is the color of the coloring agent 30, the primerfusing agent 26, 26′ is applied with the coloring agent 30. Since theprimer fusing agent 26, 26′ is clear or slightly tinted, the color ofthe coloring agent 30 will be the color of the resulting colored layer52, as the colorants of the coloring agent 30 become embedded throughoutthe coalesced/fused build material composition of the colored layer 52.The primer fusing agent 26, 26′ may be particularly suitable forobtaining lighter colors or white.

The primer fusing agent 26, 26′ and the coloring agent 30 areselectively applied in a pattern of a cross-section for the coloredlayer 52 that is to be formed (shown in FIG. 4D). In the example shownin FIG. 4C, the portion 60 is adjacent to the portion 56 of the layer 54to which the coloring agent 30 has been applied.

It is to be understood that the selective application of the primerfusing agent 26, 26′ may be accomplished in a single printing pass or inmultiple printing passes. In an example, selectively applying of theprimer fusing agent 26, 26′ is accomplished in multiple printing passes.In another example, the selectively applying of the primer fusing agent26, 26′ is accomplished in a number of printing passes ranging from 2 to4. In still another example, selectively applying of the primer fusingagent 26, 26′ is accomplished in 2 printing passes. In yet anotherexample, selectively applying of the primer fusing agent 26, 26′ isaccomplished in 4 printing passes. It may be desirable to apply theprimer fusing agent 26, 26′ in multiple printing passes to increase theamount of the energy absorber that is applied to the build materialcomposition 16, to avoid liquid splashing, to avoid displacement of thebuild material composition 16, etc.

The volume of the primer fusing agent 26, 26′ that is applied per unitof the build material composition 16 in the patterned portion 60 may besufficient to absorb and convert enough electromagnetic radiation sothat the build material composition 16 in the patterned portion 60 willcoalesce/fuse. The volume of the primer fusing agent 26, 26′ that isapplied per unit of the build material composition 16 may depend, atleast in part, on the energy absorber used, the energy absorber loadingin the primer fusing agent 26, 26′, and the build material composition16 used.

After the primer fusing agent 26, 26′ and the coloring agent 30 areselectively applied in the specific portion(s) 60 of the layer 58, theentire layer 58 of the build material composition 16 is exposed toelectromagnetic radiation (shown as EMR Exposure between FIGS. 4C and4D).

The electromagnetic radiation is emitted from the radiation source 38,38′. The length of time the electromagnetic radiation is applied for, orenergy exposure time, may be dependent, for example, on one or more of:characteristics of the radiation source 38, 38′; characteristics of thebuild material composition 16; and/or characteristics of the primerfusing agent 26, 26′.

It is to be understood that the exposing of the build materialcomposition 16 to electromagnetic radiation may be accomplished in asingle radiation event or in multiple radiation events. In an example,the exposing of the build material composition 16 is accomplished inmultiple radiation events. In another example, the exposing of the buildmaterial composition 16 to electromagnetic radiation may be accomplishedin a number of radiation events ranging from 3 to 8. In still anotherexample, the exposing of the build material composition 16 toelectromagnetic radiation may be accomplished in 3 radiation events. Itmay be desirable to expose the build material composition 16 toelectromagnetic radiation in multiple radiation events to counteract acooling effect that may be brought on by the amount of the primer fusingagent 26, 26′ that is applied to the build material layer 58.Additionally, it may be desirable to expose the build materialcomposition 16 to electromagnetic radiation in multiple radiation eventsto sufficiently elevate the temperature of the build materialcomposition 16 in the portion(s) 60, without over heating the buildmaterial composition 16 in the non-patterned portion(s).

The primer fusing agent 26, 26′ enhances the absorption of theradiation, converts the absorbed radiation to thermal energy, andpromotes the transfer of the thermal heat to the build materialcomposition 16 in contact therewith. In an example, the primer fusingagent 26, 26′ sufficiently elevates the temperature of the buildmaterial composition 16 in the layer 58 to a temperature within or abovethe melting range of the thermoplastic elastomer of the build materialcomposition 16, allowing coalescing/fusing (e.g., thermal merging,melting, binding, etc.) of the build material composition 16 to takeplace. The application of the electromagnetic radiation forms thecolored layer 52, shown in FIG. 4D.

In some examples of the methods 100, 200, 300, the electromagneticradiation has a wavelength ranging from 800 nm to 4000 nm. In anotherexample the electromagnetic radiation has a wavelength ranging from 800nm to 1400 nm. In still another example, the electromagnetic radiationhas a wavelength ranging from 800 nm to 1200 nm. Radiation havingwavelengths within the provided ranges may be absorbed (e.g., 80% ormore of the applied radiation is absorbed) by the primer fusing agent26, 26′ and may heat the build material composition 16 in contacttherewith, and may not be substantially absorbed (e.g., 25% or less ofthe applied radiation is absorbed) by the non-patterned build materialcomposition 16.

It is to be understood that portions of the build material composition16 that do not have the primer fusing agent 26, 26′ applied thereto donot absorb enough radiation to coalesce/fuse. As such, these portions donot become part of the 3D object 44′ that is ultimately formed. However,the generated thermal energy may propagate into the surrounding buildmaterial composition 16 that does not have primer fusing agent 26, 26′applied thereto. The propagation of thermal energy may be inhibited fromcoalescing/fusing the non-patterned build material composition 16 in thelayer 58, for example, when the detailing agent 42 is applied to thebuild material composition 16 in the layer 58 that are not exposed tothe primer fusing agent 26, 26′. Moreover, the propagation of thermalenergy may be inhibited from coalescing/fusing the build materialcomposition 16 in the layer 54 when the detailing agent 42 is appliedwith the coloring agent 30 in the layer 54. However, as mentioned above,some of the colored build material composition 16 in the layer 54 maybecome embedded in the adjacent surface of the coalesced/fused buildmaterial composition of the colored layer 52.

While a single colored layer 52 is shown, it is to be understood thatseveral colored layers 52 may be sequentially formed in contact with oneanother so that a color region (thicker than one voxel) is built uparound the core layer(s) 46 in the final object 44′. The outermostcolored layer 52 may form a one voxel deep shell, and the other coloredlayers may create the thicker color region. The levels of the primerfusing agent 26, 26′ and the coloring agent 30 may be higher in theoutermost colored layer 52, compared to other colored layers positionedcloser to the core layer(s) 46, in order to increase color saturation atthe exterior of the formed object 44′.

FIG. 4D also illustrates yet another layer 62 of the build materialcomposition 16, this time the layer 62 being applied to the coloredlayer 52 and to any non-coalesced/non-fused build material composition16 of layer 58. The layer 62 may be applied in the same manner as thelayers 54, 58.

Prior to further processing, the layer 62 of the build materialcomposition 16 may be exposed to pre-heating in the manner previouslydescribed.

After the layer 62 is formed, and in some instances is pre-heated, theprimer fusing agent 26, 26′ is selectively applied on portion(s) 64 ofthe build material composition 16 in the layer 62. The portion(s) 64 ofthe layer 62 will form the primer layer 48′, which is white, clear, orslightly tinted from the primer fusing agent 26, 26′. This primer layer48′ is positioned between the colored layer 52 and subsequently formedblack core layer(s) 46 in the object 44′ (see FIG. 4H). This primerlayer 48′ may be referred to as the initial layer or the first primerlayer. The primer layer 48′ optically isolates at least a portion of theblack core layer(s) 46.

In the example shown in FIG. 4D, the portion 64 to which the primerfusing agent 26, 26′ is selectively applied is adjacent to part (but notall) of the already formed colored layer 52. Selectively applying theprimer fusing agent 26, 26′ in this manner may be performed when it isdesirable to form colored layer(s) 52′ (shown in FIG. 4E) along thesides of the object 44′ that is being formed. To form the coloredlayer(s) 52′ along the sides of the object 44′, the primer fusing agent26, 26′ and the coloring agent 30 are selectively applied on otherportion(s) 66 of the build material composition 16 in the layer 62. Asan example, the portion(s) 66 may define the perimeter of thatparticular layer of the object 44′ that is being formed, and may beoutside of a perimeter or an edge boundary E (i.e., the outermostportions where the primer fusing agent 26, 26′ alone is selectivelydeposited in any build material layer) of the portion 64.

When it is desirable to form the colored layer 52′ (shown in FIG. 4E)along the sides of the object 44′ that is being formed, it may also bedesirable to selectively deposit the coloring agent 30 (with or withoutthe detailing agent 42) in portion(s) 68 of the non-patterned buildmaterial composition 16 which are adjacent to or surround the portion(s)66 (which when coalesced/fused, will form the colored layer 52′ alongthe sides of the object 44′). The colored build material composition 16in the portion(s) 68 may become embedded in coalesced/fused buildmaterial composition of the colored layer 52′. Thisnon-coalesced/non-fused, but embedded colored build material composition16 may help to maintain saturation at the surface (of the colored layer52′) by providing a colored interface between the colored layer 52′ andsurrounding non-coalesced/non-fused build material composition 16.

After the primer fusing agent 26, 26′ is applied on the portion(s) 64,and in some instances the primer fusing agent 26, 26′ and the coloringagent 30 are selectively applied on the portion(s) 66, the entire layer62 of the build material composition 16 is exposed to electromagneticradiation (shown as EMR Exposure between FIGS. 4D and 4E) in the mannerpreviously described. Exposure to electromagnetic radiation forms theprimer layer 48′, as shown in FIG. 4E.

If the primer fusing agent 26, 26′ and the coloring agent 30 areselectively applied on the portion(s) 66, the EMR exposure will formcolored layer(s) 52′ at the outer edge(s). This exposure toelectromagnetic radiation forms the colored layer(s) 52′, as shown inFIG. 4E.

The width of the colored layer(s) 52′ may be large enough to form thecolor region at this portion of the object 44′. The levels of the primerfusing agent 26, 26′, and the coloring agent 30 may be higher at theoutermost edge of the colored layer(s) 52′, compared to the innermostedge(s) of the colored layer(s) 52′, in order to increase colorsaturation at the exterior of the formed object 44′.

FIG. 4E also illustrates yet another layer 70 of the build materialcomposition 16, this time the layer 70 being applied to the primer layer48′, the colored layer(s) 52′, and to any non-coalesced/non-fused buildmaterial composition 16 of layer 62. The layer 70 may be applied in thesame manner as the layers 54, 58, 62.

Prior to further processing, the layer 70 of the build materialcomposition 16 may be exposed to pre-heating in the manner previouslydescribed.

After the layer 70 is formed, and in some instances is pre-heated, thecore fusing agent 28 is selectively applied on portion(s) 72 of thebuild material composition 16 in the layer 70. In one example, themethod 200 includes: based on a 3D object model, selectively applying acore fusing agent 28 on at least a portion 72 of a (first) layer 70 of abuild material composition 16, the build material composition 16including a thermoplastic elastomer having: an avalanche angle rangingfrom about 49 degrees to about 59 degrees; a break energy ranging fromabout 55 kJ/kg to about 78 kJ/kg; and an avalanche energy ranging fromabout 10 kJ/kg to about 27 kJ/kg.

As mentioned above, the core fusing agent 28 includes at least anaqueous or non-aqueous vehicle and an active material dispersed ordissolved therein.

It is to be understood that the selective application of the core fusingagent 28 may be accomplished in a single printing pass or in multipleprinting passes. In an example, selectively applying of the core fusingagent 28 is accomplished in multiple printing passes. In anotherexample, the selectively applying of the core fusing agent 28 isaccomplished in a number of printing passes ranging from 2 to 4. Instill another example, selectively applying of the core fusing agent 28is accomplished in 2 printing passes. In yet another example,selectively applying of the core fusing agent 28 is accomplished in 4printing passes. It may be desirable to apply the core fusing agent 28in multiple printing passes to increase the amount of the energyabsorber that is applied to the build material composition 16, to avoidliquid splashing, to avoid displacement of the build materialcomposition 16, etc.

The volume of the core fusing agent 28 that is applied per unit of thebuild material composition 16 in the patterned portion 72 may besufficient to absorb and convert enough electromagnetic radiation sothat the build material composition 16 in the patterned portion 72 willcoalesce/fuse. The volume of the core fusing agent 28 that is appliedper unit of the build material composition 16 may depend, at least inpart, on the energy absorber used, the energy absorber loading in thecore fusing agent 28, and the build material composition 16 used.

The portion(s) 72 of the layer 70 will form the core layer 46 (FIG. 4F),which may be black from the core fusing agent 28. While a single corelayer 46 is shown, it is to be understood that several core layers 46may be sequentially formed in contact with one another so that a coreregion (or part core) is built up, which makes up the bulk of the object44′. Several core layers 46 may enhance the mechanical properties of theobject 44′.

In the example shown in FIG. 4E, the portion 72 to which the core fusingagent 28 is selectively applied is adjacent to part (but not all) of thealready formed primer layer 48′. Selectively applying the core fusingagent 28 in this manner may be performed when it is desirable to formcolored layer(s) 52′ (shown in FIG. 4F) along the sides of the object44′ that is being formed. Since the core layer 46 being formed may beblack, it may also be desirable to form the primer layer 48″ between thecore layer 46 and the adjacent colored layer(s) 52′.

To form the primer layer 48″ along the perimeter of the core layer 46,the primer fusing agent 26, 26′ is selectively applied on other (orsecond) portion(s) 74 of the build material composition 16 in the layer70 that are immediately adjacent to the perimeter or edge boundary E′(i.e., the outermost portions where the core fusing agent 28 alone isselectively deposited in any build material layer) of the portion 72.The perimeter/edge boundary E′ is thus defined by the core fusing agent28. To form the colored layer(s) 52′ along/adjacent to the perimeter ofthe primer layer 48″, the primer fusing agent 26, 26′ and the coloringagent 30 are selectively applied on still other (or third) portion(s) 76of the build material composition 16 in the layer 70 that areimmediately adjacent to the perimeter or edge boundary E of the portion74 (which is defined by the primer fusing agent 26, 26′).

When it is desirable to form the colored layer(s) 52′ (shown in FIG. 4F)along the sides of the object 44′ that is being formed, it may also bedesirable to selectively deposit the coloring agent 30 (with or withoutthe detailing agent 42) in portion(s) 78 of the non-patterned buildmaterial composition 16 which are adjacent to or surround the portion(s)76 (which when coalesced/fused, will form the colored layer 52′ alongthe sides of the object 44′).

After the layer 70 is patterned in a desirable manner with at least thecore fusing agent 28, the entire layer 70 of the build materialcomposition 16 is exposed to electromagnetic radiation (shown as EMRExposure between FIGS. 4E and 4F) in the manner previously described,except that the wavelength range may be expanded to as low as 400 nmbecause some of the energy absorbers in the core fusing agent 28 canabsorb visible light as well as infrared light. In one example, themethod 200 includes: exposing the (first) layer 70 to electromagneticradiation to fuse the build material composition 16 in the at least theportion 72 of the (first) layer 70 to form a core layer 46.

The core fusing agent 28 enhances the absorption of the radiation inportion 72, converts the absorbed radiation to thermal energy, andpromotes the transfer of the thermal heat to the build materialcomposition 16 in contact therewith. In an example, the core fusingagent 28 sufficiently elevates the temperature of the build materialcomposition 16 in portion 72 to a temperature within or above themelting range of the thermoplastic elastomer of the build materialcomposition 16, allowing coalescing/fusing (e.g., thermal merging,melting, binding, etc.) of the build material composition 16 to takeplace. Exposure to electromagnetic radiation forms the core layer 46, asshown in FIG. 4F.

If the primer fusing agent 26, 26′ is selectively applied on theportion(s) 74, and the primer fusing agent 26, 26′ and the coloringagent 30 are selectively applied on the portion(s) 76, the EMR exposurewill also form primer layer(s) 48″ and colored layer(s) 52′ at the outeredge(s) of the core layer 46, as shown in FIG. 4F.

The width of the primer layer(s) 48″ may be large enough to opticallyisolate the black core layer 46.

FIG. 4F also illustrates yet another layer 80 of the build materialcomposition 16, this time the layer 80 being applied to the core layer46, the primer layer(s) 48″, the colored layer(s) 52′, and to anynon-coalesced/non-fused build material composition 16 of layer 70. Thelayer 80 may be applied in the same manner as the layers 54, 58, 62, 70.In one example, the method 200 includes: applying a second layer 80 ofthe build material composition 16 on the core layer 46.

Prior to further processing, the layer 80 of the build materialcomposition 16 may be exposed to pre-heating in the manner previouslydescribed.

After the layer 80 is formed, and in some instances is pre-heated, theprimer fusing agent 26, 26′ is selectively applied on portion(s) 82 ofthe build material composition 16 in the layer 80. In one example, themethod 200 includes: based on the 3D object model, selectively applyinga primer fusing agent 26, 26′ on at least a portion 82 of the secondlayer 80, the primer fusing agent 26, 26′ including a plasmonicresonance absorber having absorption at wavelengths ranging from 800 nmto 4000 nm and having transparency at wavelengths ranging from 400 nm to780 nm.

The portion(s) 82 of the layer 80 will form another primer layer 48′″,which is white or slightly tinted from the primer fusing agent 26, 26′.This primer layer 48′″ is positioned between the black core layer(s) 46and subsequently formed colored layer(s) 52″ in the object 44′ (see FIG.4H). As such, the primer layer 48′″ optically isolates the black corelayer(s) 46 at another end of the formed object 44′.

In the example shown in FIG. 4F, the portion 82 to which the primerfusing agent 26, 26′ is selectively applied is adjacent to the alreadyformed core layer(s) 46 and primer layer(s) 48″. Selectively applyingthe primer fusing agent 26, 26′ in this manner may be performed when itis desirable to form colored layer(s) 52′ (shown in FIG. 4G) along thesides of the object 44′ that is being formed. To form the coloredlayer(s) 52′ along the sides of the object 44′, the primer fusing agent26, 26′ and the coloring agent 30 are selectively applied on portion(s)84 of the build material composition 16 in the layer 82. As an example,the portion(s) 84 may define the perimeter of that particular layer ofthe object 44′ that is being formed, and may be outside of an edgeboundary E of the portion 82.

When it is desirable to form the colored layer 52′ (shown in FIG. 4G)along the sides of the object 44′ that is being formed, it may also bedesirable to selectively deposit the coloring agent 30 (with or withoutthe detailing agent 42) in portion(s) 86 of the non-patterned buildmaterial composition 16 which are adjacent to or surround the portion(s)84 (which when coalesced/fused, will form the colored layer 52′ alongthe sides of the object 44′).

After the primer fusing agent 26, 26′ is applied on the portion(s) 82,and in some instances the primer fusing agent 26, 26′ and the coloringagent 30, are selectively applied on the portion(s) 84, the entire layer80 of the build material composition 16 is exposed to electromagneticradiation (shown as EMR Exposure between FIGS. 4F and 4G) in the mannerpreviously described. Exposure to electromagnetic radiation forms theprimer layer 48′″, as shown in FIG. 4G. In one example, the method 200includes: exposing the second layer 80 to electromagnetic radiation tofuse the build material composition 16 in the at least the portion 82 ofthe second layer 80 to form a primer layer 48′″.

If the primer fusing agent 26, 26′ and the coloring agent 30 areselectively applied on the portion(s) 84, the EMR exposure will formcolored layer(s) 52′ at the outer edge(s) of the primer layer 48′″. Thisexposure to electromagnetic radiation forms the colored layer(s) 52′, asshown in FIG. 4G.

FIG. 4G also illustrates yet another layer 88 of the build materialcomposition 16, this time the layer 88 being applied to the primerlayer(s) 48′″ and the colored layer(s) 52′ adjacent thereto, and to anynon-coalesced/non-fused build material composition 16 of layer 80. Thelayer 88 may be applied in the same manner as the layers 54, 58, 62, 70,80. In one example, the method 200 includes: applying a third layer 88of the build material composition 16 on the primer layer 48′″.

Prior to further processing, the layer 88 of the build materialcomposition 16 may be exposed to pre-heating in the manner previouslydescribed.

After the layer 88 is formed, and in some instances is pre-heated, theprimer fusing agent 26, 26′ and the coloring agent 30 are selectivelyapplied on the same portion(s) 90 of the build material composition 16in the layer 88. In one example, the method 200 includes: based on the3D object model, selectively applying a coloring agent 30 and (i) thecore fusing agent 28 or (ii) the primer fusing agent 26, 26′ on at leasta portion 90 of the third layer 88.

The primer fusing agent 26, 26′ and the coloring agent 30 areselectively applied in a pattern of a cross-section for the coloredlayer 52″ that is to be formed (shown in FIG. 4H). In the example shownin FIG. 4G, the portion 90 is adjacent to the primer layer 48′″ and thecolored layer(s) 52′ is adjacent to the primer layer 48′″.

When the desired color for the object 44′ or a particular colored layer52″ of the object 44′ is the color of the coloring agent 30, the primerfusing agent 26, 26′ is applied with the coloring agent 30. Since theprimer fusing agent 26, 26′ is clear or slightly tinted and the buildmaterial composition 16 is white, the color of the coloring agent 30will be the color of the resulting colored layer 52″, as the colorantsof the coloring agent 30 become embedded throughout the coalesced/fusedbuild material composition of the colored layer 52″. The primer fusingagent 26, 26′ may be particularly suitable for obtaining lighter colorsor white.

It may also be desirable to selectively deposit the coloring agent 30(with or without the detailing agent 42) in portion(s) of thenon-patterned build material composition 16 which are adjacent to orsurround the portion(s) 90 (which when coalesced/fused, will form thecolored layer 52″ along the top surface of object 44′). The coloredbuild material composition 16 in the non-patterned portion(s) may becomeembedded in coalesced/fused build material composition along the sidesor edges of the colored layer 52″. The non-coalesced/non-fused, butembedded colored build material composition 16 may help to maintainsaturation at the surface (of the colored layer 52″) by providing acolored interface between the colored layer 52″ and surroundingnon-coalesced/non-fused build material composition 16.

After the primer fusing agent 26, 26′ and the coloring agent 30 areselectively applied in the specific portion(s) 90 of the layer 88, theentire layer 88 of the build material composition 16 is exposed toelectromagnetic radiation (shown as EMR Exposure between FIGS. 4G and4H). In one example, the method 200 includes: exposing the third layer88 to electromagnetic radiation to fuse the build material composition16 in the at least the portion 90 of the third layer 88 to form acolored layer 52″ having a colorant of the coloring agent 30 embeddedtherein.

The electromagnetic radiation is emitted from the radiation source 38,38′ in the manner previously described, with wavelengths suitable forthe primer fusing agent 26, 26′. Exposure to electromagnetic radiationforms the colored layer 52″, as shown in FIG. 4H, having colorants ofthe coloring agent 30 embedded therein.

While a single colored layer 52″ is shown, it is to be understood thatseveral colored layers 52″ may be sequentially formed in contact withone another so that a color region (thicker than one voxel) is built uparound the core layer(s) 46 in the final object 44′. The outermostcolored layer 52″ may form a one voxel deep shell, and the other coloredlayers may create the thicker color region. The levels of the primerfusing agent 26, 26′ and the coloring agent 30 may be higher in theoutermost colored layer 52″, compared to other colored layers positionedcloser to the core layer(s) 46, in order to increase color saturation atthe exterior of the formed object 44′.

While not shown, the coloring agent 30 may be selectively applied to thecolored layer 52″. In one example, the method 200 further comprisesapplying the coloring agent 30 on the colored layer 52″.

The coloring agent 30 applied to the colored layer 52″ may help tomaintain saturation at the surface of the colored layer 52″ by coloringthe build material composition particles at the surface, whether theseparticles are coalesced/fused, or non-coalesced/non-fused and embeddedin the coalesced/fused particles.

Also while not shown, it is to be understood that the detailing agent 42may be selectively applied on the colored layer 52″ with the coloringagent 30. In one example, the method 200 further comprises applying adetailing agent 42 with the coloring agent 30.

Throughout the methods 100, 200, 300, the color of the coloring agent 30that is applied will depend upon the desired color for the object 44′ orat least the portion of the colored layer(s) 52, 52′, 52″ to be formed.As examples, a black agent, a cyan agent, a magenta agent, or a yellowagent may be applied alone or in combination to achieve a variety ofcolors.

It to be understood that the methods 100, 200, 300 may be modified sothat the core fusing agent 28, rather than the primer fusing agent 26,26′, is applied with the coloring agent 30 to form the colored layers52, 52′, 52″. The primer fusing agent 26, 26′ may be particularlysuitable for obtaining lighter colors or white. When the desired colorfor colored layer 52 is a darker color or black, the core fusing agent28 may be applied with the coloring agent 30.

It to be further understood that the methods 100, 200, 300 may bemodified so that the sacrificial layer 54 (with the coloring agent 30thereon) and the outer colored layers 52, 52′, 52″ are not formed. Inthis modified form of the methods 100, 200, 300, the primer layer 48′would be formed first. In the resulting part, all of the primer layers48′, 48″, 48′″ would be exposed/visible, and thus would form theexterior of the part. In this example, the primer layers 48′, 48″, 48′″would form an outer white layer which encapsulates the core layer(s) 46.When the methods 100, 200, 300 are modified in this manner, the partthat is formed is white or slightly tinted (depending upon the color ofthe primer fusing agent 26, 26′).

The method 400 to form the object 44″ will now be discussed in referenceto FIGS. 5A through 5C. It is to be understood that the method 400 maybe another example of the method 100.

In FIG. 5A, a layer 94 of the build material composition 16 is appliedon the build area platform 12. The layer 94 may be applied in the samemanner as described above.

The layer 94 of the build material composition 16 may be exposed topre-heating in the manner described herein.

After the layer 94 is applied, and in some instances is pre-heated, theprimer fusing agent 26, 26′ is selectively applied on portion(s) 96 ofthe build material composition 16 in the layer 94. While the primerfusing agent 26′ is shown in FIGS. 5A and 5C, it is to be understoodthat the primer fusing agent 26 may be used instead of the primer fusingagent 26′.

The portion(s) 96 of the layer 94 will form the first layer 98 of the 3Dobject 44″ (FIG. 5C) being formed. As such, the primer fusing agent 26,26′ is selectively dispensed on the layer 94 according to a pattern of across-section for the layer 98.

After the primer fusing agent 26, 26′ is applied on the portion(s) 96,the entire layer 94 of the build material composition 16 is exposed toelectromagnetic radiation (shown as EMR Exposure between FIGS. 5A and5B) in the manner previously described.

In this example, the primer fusing agent 26, 26′ sufficiently elevatesthe temperature of the build material composition 16 in portion 96 to atemperature within or above the melting range of the thermoplasticelastomer of the build material composition 16, allowingcoalescing/fusing (e.g., thermal merging, melting, binding, etc.) of thebuild material composition 16 to take place. Exposure to electromagneticradiation forms the layer 98, as shown in FIG. 5B.

It is to be understood that portions of the build material composition16 that do not have the primer fusing agent 26, 26′ applied thereto donot absorb enough energy to coalesce/fuse.

After the layer 98 is formed, additional layer(s) (e.g., 98′, 98″, 98′″shown in FIG. 5C) may be formed thereon to create an example of the 3Dobject 44″ (shown in FIG. 5C). For example, to form the other layer 98′,additional build material composition 16 may be applied on the layer 98.The primer fusing agent 26, 26′ is then selectively applied on at leasta portion of the additional build material composition 16, according toa pattern of a cross-section for the layer (e.g., 98′) which is beingformed. After the primer fusing agent 26, 26′ is applied, the entirelayer of the additional build material composition 16 is exposed toelectromagnetic radiation in the manner previously described. Theapplication of additional build material composition 16, the selectiveapplication of the primer fusing agent 26, 26′, and the electromagneticradiation exposure may be repeated a predetermined number of cycles toform the object 44″.

In the example shown in FIGS. 5A through 5C, color may be imparted tothe entire object 44″ by applying the coloring agent 30 with the primerfusing agent 26, 26′ in each of the portions of the respective buildmaterial layers that form layers 98, 98′, 98″, 98′″.

The methods 100, 400 may end at the formation of object 44″ or color maybe imparted to the top surface of the object 44″. This is shown in FIG.5C.

To impart color, a final layer 112 of the build material composition 16is applied to the object 44″. As shown in FIG. 5C, this layer 112 isapplied to the outermost layer 98′″ of the object 44″. Prior to furtherprocessing, the layer 112 may be exposed to pre-heating in the mannerpreviously described.

After the layer 112 is formed, and in some instances is pre-heated, theprimer fusing agent 26, 26′ and the coloring agent 30 are selectivelyapplied on the same portion(s) 114 of the build material composition 16in the layer 112. The primer fusing agent 26, 26′ and the coloring agent30 are selectively applied in a pattern of a cross-section for thecolored layer that is to be formed (not shown). The color of thecoloring agent 30 that is applied will depend upon the desired color forthe part.

After the primer fusing agent 26, 26′ and the coloring agent 30 areapplied, the entire layer 112 of the build material composition 16 isexposed to electromagnetic radiation in the manner previously described.The primer fusing agent 26, 26′ sufficiently elevates the temperature ofthe build material composition 16 in the portion 114 of the layer 112 toa temperature within or above the melting range of the thermoplasticelastomer of the build material composition 16, allowingcoalescing/fusing (e.g., thermal merging, melting, binding, etc.) of thebuild material composition 16 (in contact with the primer fusing agent26, 26′) to take place. Exposure to electromagnetic radiation forms thecolored layer (not shown), having colorants of the coloring agent 30embedded therein.

It is to be understood that several colored layers may be sequentiallyformed in contact with one another so that a color region (thicker thanone voxel) is built up on the layers 98, 98′, 98″, 98′″ in the finalpart. The outermost colored layer may form a one voxel deep shell, andthe other colored layers may create the thicker color region. The levelsof the primer fusing agent 26, 26′ and the coloring agent 30 may behigher in the outermost colored layer, as compared to other coloredlayers positioned closer to the layer 98′″, in order to increase colorsaturation at the exterior of the formed object 44′″.

While not shown, the coloring agent 30 may be selectively applied to thecolored layer. The coloring agent 30 applied to the colored layer mayhelp to maintain saturation at the surface of the colored layer bycoloring the build material composition particles at the surface,whether these particles are coalesced/fused or non-coalesced/non-fusedand embedded in the coalesced/fused particles.

It is to be understood that the methods 100, 400 may also be modifiedsimilarly to the method 300 in order to form colored layers (e.g., 52and 52′) so that the part is completely encapsulated by colored layers.

Another example method 500 to form a 3D object will now be discussed inreference to FIGS. 6A and 6B. It is to be understood that the method 500may be another example of the method 100.

In FIG. 6A, a layer 95 of the build material composition 16 is appliedon the build area platform 12. The layer 95 may be applied in the samemanner as described above.

The layer 95 of the build material composition 16 may be exposed topre-heating in the manner described herein.

After the layer 95 is applied, and in some instances is pre-heated, thecore fusing agent 28 is selectively applied on portion(s) 97 of thebuild material composition 16 in the layer 95. The portion(s) 97 of thelayer 95 will form the first layer 99 of the 3D object being formed (notshown). As such, the core fusing agent 28 is selectively dispensed onthe layer 95 according to a pattern of a cross-section for the layer 99.

After the core fusing agent 28 is applied on the portion(s) 97, theentire layer 95 of the build material composition 16 is exposed toelectromagnetic radiation (shown as EMR Exposure between FIGS. 6A and6B) in the manner previously described.

In this example, the core fusing agent 28 sufficiently elevates thetemperature of the build material composition 16 in portion 97 to atemperature within or above the melting range of the thermoplasticelastomer of the build material composition 16, allowingcoalescing/fusing (e.g., thermal merging, melting, binding, etc.) of thebuild material composition 16 to take place. Exposure to electromagneticradiation forms the layer 99, as shown in FIG. 5B.

It is to be understood that portions of the build material composition16 that do not have the core fusing agent 28 applied thereto do notabsorb enough energy to coalesce/fuse.

After the layer 99 is formed, additional layer(s) may be formed thereonto create an example of the 3D object. For example, to form anotherlayer, additional build material composition 16 may be applied on thelayer 99. The core fusing agent 28 is then selectively applied on atleast a portion of the additional build material composition 16,according to a pattern of a cross-section for the layer which is beingformed. After the core fusing agent 28 is applied, the entire layer ofthe additional build material composition 16 is exposed toelectromagnetic radiation in the manner previously described. Theapplication of additional build material composition 16, the selectiveapplication of the core fusing agent 28, and the electromagneticradiation exposure may be repeated a predetermined number of cycles toform the part.

In the example shown in FIGS. 6A and 6B, color may be imparted to theentire object 44″ by applying the coloring agent 30 with the core fusingagent 28 in each of the portions of the respective build material layersthat form layers of the part.

It is to be understood that the methods 100, 500 may also be modifiedsimilarly to the method 300 in order to form colored layers (e.g., 52,52′, 52″) so that the part is completely encapsulated by colored layers.

In any of the examples disclosed herein, when the 3D object 44, 44′, 44″is complete, it may be removed from the build material platform 12, andany non-coalesced/non-fused build material composition 16 may be removedfrom the 3D object 44, 44′, 44″.

In any of the methods 100, 200, 300, 400, 500 disclosed herein, thenon-patterned and non-coalesced/non-fused build material composition 16may be reclaimed to be reused as build material in the printing ofanother 3D object. In some examples, the methods 100, 200, 300, 400, 500may be accomplished in an air environment. As used herein, an “airenvironment” or an “environment containing air” refers to an environmentthat contains 20 vol % or more of oxygen.

Printing System

Referring now to FIG. 7, an example of a 3D printing system 10 isschematically depicted. It is to be understood that the 3D printingsystem 10 may include additional components (some of which are describedherein) and that some of the components described herein may be removedand/or modified. Furthermore, components of the 3D printing system 10depicted in FIG. 7 may not be drawn to scale and thus, the 3D printingsystem 10 may have a different size and/or configuration other than asshown therein.

In an example, the three-dimensional (3D) printing system 10, comprises:a supply 14 of a build material composition 16 including a thermoplasticelastomer having: an avalanche angle ranging from about 49 degrees toabout 59 degrees; a break energy ranging from about 55 kJ/kg to about 78kJ/kg; and an avalanche energy ranging from about 10 kJ/kg to about 27kJ/kg; a build material distributor 18; a supply of a fusing agent 26,26′, 28; a first applicator 24A, 24B for selectively dispensing thefusing agent 26, 26′, 28; a source 38, 38′ of electromagnetic radiation;a controller 36; and a non-transitory computer readable medium havingstored thereon computer executable instructions to cause the controller36 to: utilize the build material distributor 18 to dispense the buildmaterial composition 16; utilize the first applicator 24A, 24B toselectively dispense the fusing agent 26, 26′, 28 on at least a portionof the build material composition 16; and utilize the source 38, 38′ ofelectromagnetic radiation to expose the build material composition 16 toradiation to coalesce/fuse the at least the portion of the buildmaterial composition 16. Any example of the build material composition16 may be used in the examples of the system 10.

In some examples, the 3D printing system 10 may further include a supplyof another fusing agent 26, 26′, 28; and another applicator 24A, 24B forselectively dispensing the other fusing agent 26, 26′, 28. In theseexamples, the computer executable instructions may further cause thecontroller 36 to utilize the other applicator 24A, 24B to selectivelydispense the other fusing agent 26, 26′, 28.

In some other examples, the 3D printing system 10 may further include asupply of a coloring agent 30; and another applicator 24C forselectively dispensing the coloring agent 30. In these examples, thecomputer executable instructions may further cause the controller 36 toutilize the other applicator 24C to selectively dispense the coloringagent 30.

While not shown in FIG. 7, in still some other examples, the 3D printingsystem 10 may further include a supply of a detailing agent 42; andanother applicator for selectively dispensing the detailing agent 42. Inthese examples, the computer executable instructions may further causethe controller 36 to utilize the other applicator to selectivelydispense the detailing agent 42.

As shown in FIG. 7, the printing system 10 includes the build areaplatform 12, the build material supply 14 containing the build materialcomposition 16 including the thermoplastic elastomer disclosed herein,and the build material distributor 18.

As mentioned above, the build area platform 12 receives the buildmaterial composition 16 from the build material supply 14. The buildarea platform 12 may be integrated with the printing system 10 or may bea component that is separately insertable into the printing system 10.For example, the build area platform 12 may be a module that isavailable separately from the printing system 10. The build materialplatform 12 that is shown is one example, and could be replaced withanother support member, such as a platen, a fabrication/print bed, aglass plate, or another build surface.

As also mentioned above, the build material supply 14 may be acontainer, bed, or other surface that is to position the build materialcomposition 16 between the build material distributor 18 and the buildarea platform 12. In some examples, the build material supply 14 mayinclude a surface upon which the build material composition 16 may besupplied, for instance, from a build material source (not shown) locatedabove the build material supply 14. Examples of the build materialsource may include a hopper, an auger conveyer, or the like.Additionally, or alternatively, the build material supply 14 may includea mechanism (e.g., a delivery piston) to provide, e.g., move, the buildmaterial composition 16 from a storage location to a position to bespread onto the build area platform 12 or onto a previously formed layerof the 3D object. Another example of the mechanism for moving the buildmaterial composition 16 is a pneumatic conveying system.

As also mentioned above, the build material distributor 18 may be ablade (e.g., a doctor blade), a roller, a combination of a roller and ablade, and/or any other device capable of spreading the build materialcomposition 16 over the build area platform 12 (e.g., a counter-rotatingroller).

As shown in FIG. 7, the printing system 10 may include the applicator24A, which may contain the fusing agent 26, 26′. As also shown, theprinting system 10 may further include the applicator 24B, which maycontain the fusing agent 28, and/or the applicator 24C, which maycontain the coloring agent 30. While not shown, the printing system 10may further include another applicator (which may contain the detailingagent 42).

The applicator(s) 24A, 24B, 24C may be scanned across the build areaplatform 12 in the directions indicated by the arrow 32, e.g., along they-axis. The applicator(s) 24A, 24B, 24C may be, for instance, a thermalinkjet printhead, a piezoelectric printhead, a continuous inkjetprinthead, etc., and may extend a width of the build area platform 12.While the each applicator 24A, 24B, 24C is shown in FIG. 7 as a singleapplicator, it is to be understood that each applicator 24A, 24B, 24Cmay include multiple applicators that span the width of the build areaplatform 12. Additionally, the applicators 24A, 24B, 24C may bepositioned in multiple printbars. The applicator(s) 24A, 24B, 24C mayalso be scanned along the x-axis, for instance, in configurations inwhich the applicator(s) 24A, 24B, 24C do/does not span the width of thebuild area platform 12 to enable the applicator(s) 24A, 24B, 24C todeposit the respective agents 26, 26′, 28, 30, 42 over a large area ofthe build material composition 16. The applicator(s) 24A, 24B, 24C maythus be attached to a moving XY stage or a translational carriage(neither of which is shown) that moves the applicator(s) 24A, 24B, 24Cadjacent to the build area platform 12 in order to deposit therespective agents 26, 26′, 28, 30, 42 in predetermined areas of thebuild material layer(s) that has/have been formed on the build areaplatform 12 in accordance with the methods 100, 200, 300, 400, 500disclosed herein. The applicator(s) 24A, 24B, 24C may include aplurality of nozzles (not shown) through which the respective agents 26,26′, 28, 30, 42 are to be ejected.

The applicator(s) 24A, 24B, 24C may deliver drops of the respectiveagents 26, 26′ 28, 30, 42 at a resolution ranging from about 300 dotsper inch (DPI) to about 1200 DPI. In other examples, the applicator(s)24A, 24B, 24C may deliver drops of the respective agents 26, 26′, 28,30, 42 at a higher or lower resolution. The drop velocity may range fromabout 10 m/s to about 24 m/s and the firing frequency may range fromabout 1 kHz to about 48 kHz. In one example, the volume of each drop maybe on the order of about 3 picoliters (pL) to about 18 pL, although itis contemplated that a higher or lower drop volume may be used. In someexamples, the applicator(s) 24A, 24B, 24C is/are able to delivervariable drop volumes of the respective agents 26, 26′, 28, 30, 42. Oneexample of a suitable printhead has 600 DPI resolution and can deliverdrop volumes ranging from about 6 pL to about 14 pL.

Each of the previously described physical elements may be operativelyconnected to a controller 36 of the printing system 10. The controller36 may process print data that is based on a 3D object model of the 3Dobject/part to be generated. In response to data processing, thecontroller 36 may control the operations of the build area platform 12,the build material supply 14, the build material distributor 18, and theapplicator(s) 24A, 24B, 24C. As an example, the controller 36 maycontrol actuators (not shown) to control various operations of the 3Dprinting system 10 components. The controller 36 may be a computingdevice, a semiconductor-based microprocessor, a central processing unit(CPU), an application specific integrated circuit (ASIC), and/or anotherhardware device. Although not shown, the controller 36 may be connectedto the 3D printing system 10 components via communication lines.

The controller 36 manipulates and transforms data, which may berepresented as physical (electronic) quantities within the printer'sregisters and memories, in order to control the physical elements tocreate the 3D object. As such, the controller 36 is depicted as being incommunication with a data store 34. The data store 34 may include datapertaining to a 3D object to be printed by the 3D printing system 10.The data for the selective delivery of the build material composition16, the fusing agent 26, 26′, 28, etc. may be derived from a model ofthe 3D object to be formed. For instance, the data may include thelocations on each build material layer that the first applicator 24A,24B is to deposit the fusing agent 26, 26′, 28. In one example, thecontroller 36 may use the data to control the first applicator 24A, 24Bto selectively apply the fusing agent 26, 26′, 28. The data store 34 mayalso include machine readable instructions (stored on a non-transitorycomputer readable medium) that are to cause the controller 36 to controlthe amount of build material composition 16 that is supplied by thebuild material supply 14, the movement of the build area platform 12,the movement of the build material distributor 18, the movement of theapplicator(s) 24A, 24B, 24C, etc.

As shown in FIG. 7, the printing system 10 may also include a source 38,38′ of electromagnetic radiation. In some examples, the source 38 ofelectromagnetic radiation may be in a fixed position with respect to thebuild material platform 12. The source 38 in the fixed position may be aconductive heater or a radiative heater that is part of the printingsystem 10. These types of heaters may be placed below the build areaplatform 12 (e.g., conductive heating from below the platform 12) or maybe placed above the build area platform 12 (e.g., radiative heating ofthe build material layer surface). In other examples, the source 38′ ofelectromagnetic radiation may be positioned to apply radiation to thebuild material composition 16 immediately after the fusing agent 26,26′, 28 has been applied thereto. In the example shown in FIG. 7, thesource 38′ of electromagnetic radiation is attached to the side of theapplicators 24A, 24B, 24C which allows for patterning andheating/exposing to radiation in a single pass.

The source 38, 38′ of electromagnetic radiation may emit radiationhaving wavelengths ranging from about 400 nm to about 4000 nm. As oneexample, the electromagnetic radiation may range from about 800 nm toabout 1400 nm. As another example, the electromagnetic radiation mayrange from about 400 nm to about 1200 nm. As still another example, theelectromagnetic radiation may be blackbody radiation with a maximumintensity at a wavelength of about 1100 nm. The source 38, 38′ ofelectromagnetic radiation may be infrared (IR) or near-infrared lightsources, such as IR or near-IR curing lamps, IR or near-IR lightemitting diodes (LED), or lasers with the desirable IR or near-IRelectromagnetic wavelengths.

The source 38, 38′ of electromagnetic radiation may be operativelyconnected to a lamp/laser driver, an input/output temperaturecontroller, and temperature sensors, which are collectively shown asradiation system components 40. The radiation system components 40 mayoperate together to control the source 38, 38′ of electromagneticradiation. The temperature recipe (e.g., radiation exposure rate) may besubmitted to the input/output temperature controller. During heating,the temperature sensors may sense the temperature of the build materialcomposition 16, and the temperature measurements may be transmitted tothe input/output temperature controller. For example, a thermometerassociated with the heated area can provide temperature feedback. Theinput/output temperature controller may adjust the source 38, 38′ ofelectromagnetic radiation power set points based on any differencebetween the recipe and the real-time measurements. These power setpoints are sent to the lamp/laser drivers, which transmit appropriatelamp/laser voltages to the source 38, 38′ of electromagnetic radiation.This is one example of the radiation system components 40, and it is tobe understood that other radiation source control systems may be used.For example, the controller 36 may be configured to control the source38, 38′ of electromagnetic radiation.

To further illustrate the present disclosure, an example is givenherein. It is to be understood that this example is provided forillustrative purposes and is not to be construed as limiting the scopeof the present disclosure.

Example

Two examples of the build material composition disclosed herein wereprepared. The first example build material composition (labeled “PEBA”in Table 1) included a polyether block amide as the thermoplasticelastomer. The second example build material composition (labeled “TPU”in Table 1) included a thermoplastic polyurethane as the thermoplasticelastomer. Each example build material included less than 5 wt % ofadditives (i.e., antioxidant(s), whitener(s), antistatic agent(s), andflow aid(s)).

The avalanche angle, the break energy, the avalanche energy, and thedynamic density of each of the example build material compositions(i.e., each of the example thermoplastic elastomers) were measured usinga REVOLUTION™ instrument (from Mercury Scientific Inc.). Each of theavalanche angle, the break energy, the avalanche energy, and the dynamicdensity was measured over 100 avalanches at room temperature using a 100cc sample of the example build material composition, a rotation rate of0.3 RPM, an imaging rate of 10 FPS, a prep time of 60 seconds, and anavalanche threshold of 0.65%. The results of these measurements areshown in Table 1.

TABLE 1 Example Avalanche Break Avalanche Dynamic build material Angleenergy energy density composition (degrees) (kJ/kg) (kJ/kg) (g/cc) PEBA57 73 22 0.36 TPU 51 60 15 0.34

The dynamic density of the first example build material composition(i.e., the example thermoplastic elastomer) was within 15% of the bulkdensity of the first example build material composition (i.e., ±15% ofthe bulk density of the first example build material composition). Thedynamic density of the second example build material compositions wasalso within 15% of the bulk density of the second example build materialcompositions (i.e., ±15% of the bulk density of the second example buildmaterial composition).

Several 3D objects were printed with each of the example build materialcompositions using examples of the 3D printing methods disclosed herein.Several 3D objects were printed with each of the example build materialcompositions (PEBA and TPU) on a small test bed printer with an examplefusing agent that included carbon black as the energy absorber.Additionally, several 3D objects were printed with the first examplebuild material composition (PEBA) on a large format 3D printer with theexample fusing agent (that included carbon black as the energyabsorber). The fusing agent was not modified for the various buildmaterials. For the 3D objects formed with the first example buildmaterial composition, the fusing agent was dispensed at a fluid densityranging from about 7 ng per 1/600 inch² to about 14 ng per 1/600 inch².In this example, the fluid density depended, in part, on whether thesmall test bed or large format 3D printer was used and on the geometryof the 3D object being formed. For the 3D objects formed with the secondexample build material composition, the fusing agent was dispensed at afluid density of about 9 ng per 1/600 inch². In other examples, it is tobe understood that the fluid density may be higher or lower than thosevalues presented in this example. For example, the fluid density mayrange from about 3.5 ng per 1/600 inch² to about 30 ng per 1/600 inch².

Each of the example build material compositions was able to be spreadinto substantially uniform build material layers. Each of the 3D objectswas sufficiently fused/coalesced. Further, the non-patterned buildmaterial adjacent to each of the 3D objects was able to be removed andseparated from the completed 3D object. Thus, each of the example buildmaterial compositions was shown to be a suitable build materialcomposition for the 3D printing methods disclosed herein.

Additionally, ultimate tensile strength, the % strain at break, and thetear strength of the 3D objects formed with the first example buildmaterial composition on the large format 3D printer were measured usingInstron testing equipment. The average values for each of thesemeasurements are shown in Table 2.

TABLE 2 Build material Ultimate Tensile Strain at Tear Strengthcomposition used to Strength (MPa) Break (%) (N/mm) form the 3D objectsAvg. Std. Dev. Avg. Std. Dev. Avg. Std. Dev. PEBA 8.50 0.84 346.05 67.8357.54 7.39

As shown in Table 2, the mechanical properties (i.e., ultimate tensilestrength, strain at break, and tear strength) of the 3D objects formedfrom the first example build material composition are acceptable for 3Dprinted objects. Thus, these results further indicate that the firstexample build material composition is a suitable build materialcomposition for the 3D printing methods disclosed herein withoutadjusting the fusing agent composition.

It is to be understood that the ranges provided herein include thestated range and any value or sub-range within the stated range. Forexample, from about 55 kJ/kg to about 78 kJ/kg should be interpreted toinclude not only the explicitly recited limits of from about 55 kJ/kg toabout 78 kJ/kg, but also to include individual values, such as about58.5 kJ/kg, about 63.67 kJ/kg, about 70.74 kJ/kg, about 77 kJ/kg, etc.,and sub-ranges, such as from about 63 kJ/kg to about 70 kJ/kg, fromabout 55.5 kJ/kg to about 62.7 kJ/kg, from about 68.71 kJ/kg to about75.79 kJ/kg, etc. Furthermore, when “about” is utilized to describe avalue, this is meant to encompass minor variations (up to +/−10%) fromthe stated value.

Reference throughout the specification to “one example”, “anotherexample”, “an example”, and so forth, means that a particular element(e.g., feature, structure, and/or characteristic) described inconnection with the example is included in at least one exampledescribed herein, and may or may not be present in other examples. Inaddition, it is to be understood that the described elements for anyexample may be combined in any suitable manner in the various examplesunless the context clearly dictates otherwise.

In describing and claiming the examples disclosed herein, the singularforms “a”, “an”, and “the” include plural referents unless the contextclearly dictates otherwise.

While several examples have been described in detail, it is to beunderstood that the disclosed examples may be modified. Therefore, theforegoing description is to be considered non-limiting.

What is claimed is:
 1. A three-dimensional (3D) printing kit,comprising: a build material composition including a thermoplasticelastomer having: an avalanche angle ranging from about 49 degrees toabout 59 degrees; a break energy ranging from about 55 kJ/kg to about 78kJ/kg; and an avalanche energy ranging from about 10 kJ/kg to about 27kJ/kg; and a fusing agent to be applied to at least a portion of thebuild material composition during 3D printing, the fusing agentincluding an energy absorber to absorb electromagnetic radiation tocoalesce the thermoplastic elastomer in the at least the portion.
 2. The3D printing kit as defined in claim 1 wherein the thermoplasticelastomer has a dynamic density within about 15% of a bulk density ofthe thermoplastic elastomer.
 3. The 3D printing kit as defined in claim1 wherein one of: (i) the thermoplastic elastomer is a polyether blockamide, the avalanche angle ranges from about 55 degrees to about 59degrees, the break energy ranges from about 68 kJ/kg to about 78 kJ/kg,and the avalanche energy ranges from about 17 kJ/kg to about 27 kJ/kg;or (ii) the thermoplastic elastomer is a thermoplastic polyurethane, theavalanche angle ranges from about 49 degrees to about 53 degrees, thebreak energy ranges from about 55 kJ/kg to about 65 kJ/kg, and theavalanche energy ranges from about 10 kJ/kg to about 20 kJ/kg.
 4. The 3Dprinting kit as defined in claim 1 wherein the thermoplastic elastomeris a polyether block amide having a dynamic density of about 0.36 g/cc.5. The 3D printing kit as defined in claim 1, further comprising acoloring agent selected from the group consisting of a black agent, acyan agent, a magenta agent, and a yellow agent.
 6. The 3D printing kitas defined in claim 1, further comprising a detailing agent including asurfactant, a co-solvent, and water.
 7. The 3D printing kit as definedin claim 1 wherein the fusing agent is a core fusing agent and theenergy absorber has absorption at least at wavelengths ranging from 400nm to 780 nm.
 8. The 3D printing kit as defined in claim 7, furthercomprising a primer fusing agent including a plasmonic resonanceabsorber having absorption at wavelengths ranging from 800 nm to 4000 nmand having transparency at wavelengths ranging from 400 nm to 780 nm. 9.The 3D printing kit as defined in claim 1 wherein the fusing agent is aprimer fusing agent and the energy absorber is a plasmonic resonanceabsorber having absorption at wavelengths ranging from 800 nm to 4000 nmand having transparency at wavelengths ranging from 400 nm to 780 nm.10. A method for using the three-dimensional (3D) printing kit asdefined in claim 1, the method comprising: applying the build materialcomposition to form a build material layer; based on a 3D object model,selectively applying the fusing agent on at least a portion of the buildmaterial layer; and exposing the build material layer to electromagneticradiation to coalesce the build material composition in the at least theportion to form a layer of a 3D object.
 11. The method as defined inclaim 10, further comprising: iteratively applying individual buildmaterial layers of the build material composition; based on the 3Dobject model, selectively applying the fusing agent to at least some ofthe individual build material layers to define individually patternedlayers, wherein the fusing agent is selected from the group consistingof a core fusing agent, a primer fusing agent, or both the core fusingagent and the primer fusing agent; and iteratively exposing theindividually patterned layers to the electromagnetic radiation to formindividual object layers, wherein each of the individual object layersis selected from the group consisting of a core layer, a primer layer,or a layer including a core portion and a primer portion.
 12. The methodas defined in claim 10, wherein: the fusing agent is a core fusingagent; exposing the layer to electromagnetic radiation forms a corelayer; and the method further comprises: applying a second layer of thebuild material composition on the core layer; based on the 3D objectmodel, selectively applying a primer fusing agent on at least a portionof the second layer, the primer fusing agent including a plasmonicresonance absorber having absorption at wavelengths ranging from 800 nmto 4000 nm and having transparency at wavelengths ranging from 400 nm to780 nm; and exposing the second layer to electromagnetic radiation tofuse the build material composition in the at least the portion of thesecond layer to form a primer layer.
 13. The method as defined in claim12, further comprising: applying a third layer of the build materialcomposition on the primer layer; based on the 3D object model,selectively applying a coloring agent and (i) the core fusing agent or(ii) the primer fusing agent on at least a portion of the third layer;and exposing the third layer to electromagnetic radiation to fuse thebuild material composition in the at least the portion of the thirdlayer to form a colored layer having a colorant of the coloring agentembedded therein.
 14. A three-dimensional (3D) printing composition,comprising: a build material including a thermoplastic elastomer having:an avalanche angle ranging from about 49 degrees to about 59 degrees; abreak energy ranging from about 55 kJ/kg to about 78 kJ/kg; and anavalanche energy ranging from about 10 kJ/kg to about 27 kJ/kg; and afusing agent to be applied to at least a portion of the build materialduring 3D printing, the fusing agent including an energy absorber havingabsorption at least at some wavelengths ranging from 400 nm to 4000 nmto absorb electromagnetic radiation to coalesce the thermoplasticelastomer in the at least the portion.
 15. The 3D printing compositionas defined in claim 14 wherein the thermoplastic elastomer has a dynamicdensity within about 15% of a bulk density of the thermoplasticelastomer.